Thia (oxa) diazole derivatives

ABSTRACT

Thia-diazole derivatives having the following partial structural formula had selective herbicidal activity on some crops. A process for producing these compounds is also disclosed: ##STR1##

The present invention relates to thia (oxa) diazole derivatives, herbicidal compositions in the form of mixture of such compound(s) with inert carrier(s), and processes for the production of such compounds.

In many cases of agricultural or horticultural cultivation, many kinds and amount of herbicides have come to be used for weed control in order to save the labor of removing weeds in the fields, however, in some occasion, phytotoxicity of herbicides may injure crops, or herbicides remaining in the field may cause environmental pollution.

Consequently, chemicals possessing greater efficacy and higher safty to mammal have been awaited to be developed.

3H-thiazolo-(2,3-c)-1,2,4-thiadiazole having the following formula: ##STR2## which are similar to but different from the compounds of the present invention at the point that it has double bond on thiazole ring have been reported on J. Org. Chem. 1975 40 (18) 2600-2604.

Also, compounds having the following formula and a process for the preparation thereof: ##STR3## wherein r₁ is H, CH₃ S-- or CH₃ SO--, and r₂ is H, or Cl, are described together with their medical fungicidal activity in J. Pharm. Sci. 1979, 68 (2) 182-185.

The Inventors of this invention, studied many thia-diazole derivatives in order to find a compound having herbicidal activity. As a result, they found that a group of compounds having the following partial structure formula: ##STR4## had herbicidal activity and exhibited selectivity on some crops, though said known compounds having doble bond(s) on the thiazole ring contained in the thiazolo (2,3-C) 1,2,4-thiadiazole ring do not have herbicidal activity.

The inventors, further, carried out investigation about the relation between the structure of the condensed ring of the compounds having the following partial structure formula: ##STR5## and the herbicidal activity thereof.

As the results, they found that almost all of the compounds having the condensed ring in the formula (II) wherein X represents ##STR6## and Y represents S, or O exhibited the excellent herbicidal activity.

On said condensed ring, substituent(s) of hydroxy, C₁₋₈ hydrocarbon which may be substituted by halogen, C₁₋₈ hydrocarbon-oxy or C₁₋₈ hydrocarbon-thio, C₁₋₈ hydrocarbon-carbonyloxy, C₁₋₈ hydrocarbon-oxycarbonyl or C₁₋₈ alkylidene, wherein hydrocarbon means and includes linear, branched or cyclic alkyl, alkenyl or alkynyl; or aryl aralkyl or alkylaryl, are preferred. For the substituents, it looks like the too bulky ones tend to decrease the herbicidal activity.

The inventors conducted further extensive investigation on the relation between the substituent(s) on the phenyl radical (right part of the formula (II) and herbicidal activity and selectivity thereof.

In order to easily explain in detail of said substituents, said substituted phenyl radical is shown as ##STR7##

As the results of the investigation, they found that a substituted phenyl radical of the formula ##STR8## which is explained in detail in the followings, exhibited herbicidal activity and selectivity by joining with the residue of the condensed ring of formula (III) as below: ##STR9## wherein

R represents same or different substituent(s) selected from the group consisting of halogen, nitro, cyano, --G--R¹, ##STR10## di-C₁₋₈ hydrocarbon-sulfamoyl and --L; and

n represents an integer of 1 to 5; and

wherein G represents ##STR11## in which r¹⁰ represents hydrogen or C₁₋₈ hydrocarbon radical; and

R¹ represents hydrogen, ##STR12## heterocyclic radical containing oxygen or nitrogen or --T; and

K represents oxygen or sulfur; and

R² represents hydrogen, metal corresponding to one valency, C₁₋₈ alkylidene amino or --U; and

each of R³ and R⁴ represents hydrogen, C₁₋₈ hydrocarbon radical, or C₁₋₈ hydrocarbon-oxy; and

R⁵ represents C₁₋₈ hydrocarbon radical which may be substituted by hydrocabon-oxy; and

R⁶ represents hydrogen, or C₁₋₈ hydrocarbon radical, which may be substituted by C₁₋₈ hydrocarbon-oxycarbonyl; and

R⁷ represents hydrogen or C₁₋₈ hydrocarbon radical; and

--L represents C₁₋₈ hydrocarbon radical which may be substituted by halogen, hydroxy, cyano, ##STR13## C₁₋₈ hydrocarbon-oxy, C₁₋₈ hydrocarbon-carbonyloxy or ##STR14## and wherein each of r¹¹, r¹² and r¹³ represents C₁₋₈ hydrocarbon radical; and

r¹⁴ represents C₁₋₁₂ hydrocarbon radical; and

r¹⁵ represents C₁₋₁₂ hydrocarbon radical which may be substituted by halogen or C₁₋₈ hydrocarbon-oxycarbonyl; and

each of r¹⁶ and r¹⁷ represents hydrogen or C₁₋₈ hydrocarbon radical; and

--T represents C₁₋₁₆ hydrocarbon radical which may be substituted by halogen, nitro, cyano, --Q--r²¹, C₁₋₈ hydrocarbon-carbonyloxy, tri-C₁₋₈ alkylsilyl, ##STR15## or heterocyclic radical containing nitrogen; and

--U represents C₁₋₁₂ hydrocarbon which may be substituted by cyano, C₁₋₈ hydrocarbon-oxycarbonyl, C₁₋₈ hydrocarbon-oxy, C₁₋₈ hydrocarbon-thio, tri-C₁₋₈ alkylsilyl or --O(CH₂)_(g) --_(h) Or²⁸ ; and

r¹⁸ represents hydrogen, metal corresponding to one valency or C₁₋₁₀ hydrocarbon radical; and

each of r¹⁹ and r²⁰ represents C₁₋₈ hydrocarbon radical:

wherein

Q represents --O-- or --S(O)_(k) -- (k=0, 1 or 2); and

r²¹ represents hydrogen or C₁₋₁₂ hydrocarbon radical, which may be substituted by C₁₋₈ hydrocarbon-oxy, C₁₋₈ hydrocarbon-oxycarbonyl, halogen, nitro or methylendioxy, or C₁₋₈ hydrocarbon-carbamoyl; and

W represents oxygen or sulfur; and

r²² represents hydrogen, metal corresponding to one valency, C₁₋₈ alkylidene amino, or C₁₋₁₆ hydrocarbon radical which may be substituted by halogen, C₁₋₁₂ hydrocarbon-oxy, C₁₋₁₂ hydrocarbon-thio, C₁₋₈ hydrocarbon-carbonyl, C₁₋₈ hydrocarbon-oxy-carbonyl-C₁₋₈ hydrocarbon-thio, heterocyclic radical containing oxygen (which may be substituted by C₁₋₈ hydrocarbon radical) tri-C₁₋₈ alkylsilyl or cyano; and

Z represents oxygen or sulfur; and

each of r²³ and r²⁴ represents hydrogen, C₁₋₈ hydrocarbon-oxy, C₁₋₈ hydrocarbon-carbamoyl, C₁₋₁₂ hydrocarbon radical, which may be substituted by C₁₋₈ hydrocarbon-oxy or C₁₋₈ hydrocarbon-oxycarbonyl; and

r²⁵ represents C₁₋₈ hydrocarbon radical; or heterocyclic radical containing nitrogen; and

r²⁶ represents hydrogen, C₁₋₈ hydrocarbon radical or C₁₋₈ hydrocarbon-carbonyl which may be substituted by halogen; and

r²⁷ represents amino, or C₁₋₈ hydrocarbon radical; and

g represents an integer of 1 to 5; and

h represents an integer of 2 to 10, and

r²⁸ represents C₁₋₈ hydrocarbon radical:

In the course of said investigation, the inventors found that the phenyl radical substituted by halogen at 4-position gave high herbicidal activity to the compound and said phenyl radical substituted by halogen having --O(or S)--T or --COK--U (T, K and U have the same meaning as above-mentioned) at 3 or 5-position gave higher herbicidal activity, and further 2--F--4--Cl--5--O(or S)--T or 2--F--4--Cl--5--COK--U phenyl radical created the highest grade herbicidal activity within this invention, by joining with said condensed ring (III).

According to the first aspect of the present invention, there is provided a compound having the formula: ##STR16## wherein X represents --D--E--; and ##STR17##

each of r¹ to r⁹ : hydroxy, C₁₋₈ hydrocarbon radical which may be substituted by halogen, C₁₋₈ hydrocarbon-oxy or C₁₋₈ hydrocarbon-thio, C₁₋₈ hydrocarbon-carbonyloxy or C₁₋₈ hydrocarbon-oxycarbonyl, and r¹, r², r³, r⁴, r⁵, r⁶, r⁷, r⁸ and r⁹ may form ring(s) or C₁₋₈ alkylidene(s) by joining each other.

Y represents ##STR18## and each of R and n represents as same as above-mentioned.

In this invention and in the claims of this invention, the word "hydorcarbon" or "hydrocarbon radical" means and includes linear, branched or cyclic alkyl, alkenyl or alkynyl; or aryl, aralkyl or alkylaryl. And "heterocyclic radical containing nitrogen means heterocyclic radical containing nitrogen in which oxygen and/or sulfur atom(s) may be contained, and "heterocyclic radical containing oxygen" means hetrocyclic radical containing oxygen in which nitrogen atom(s) may be contained.

According to the second aspect of the present invention there is provided a herbicidal composition comprising an inert carrier and an effective amount of the compound having the formula (IV).

The compounds of the present invention have little phytotoxicities to the crops such as corn, wheat, soybeans, peanuts, alfalfa, etc., while they possesses superior herbicidal activity against wide varieties of weeds such as common lambsquater, redroot pigweed, flatsedge, etc., irrespective of their growth stage. Particularly, the compounds show higher herbicidal activity in post emergence treatment.

The group of compounds having the formula (IV), in which X represents --CH₂ -- and Y represents S and (R)n represents 2--F--4--Cl 5-substituted by alkoxycarbonylalkoxy, alkoxycarbonylalkoxylcarbonyl or alkoxycarbonylalkylthio, exhibited the highest herbicidal activity and selectivity for soybeans in post emergence treatment.

The compounds also exhibit high selectivity on rice plant and high herbicidal activity against barnyardgrass, monochoria, smallflower unbrella sedge, etc., regardless of their growth stage. Particularly, compounds having 2--F--4--Cl--5--C₁₋₈ alkynyloxyphenyl radical exhibit higher selectivity and activity.

Further, they can be applied for the control of the weeds in orchards, lawn, roadway sides, vacant lots, etc.

According to a third aspect of the present invention, there is provided a process for the preparation of the compound of the formula (IV), comprising the step of reaction is illustrated by the following equation.

1. in case Y being sulfur and X being E (5 membered ring): ##STR19##

A compound having the formula (V) is reacted with a compound having the formula (VI) in an inert solvent, for example, ether, methylene dichloride, chloroform, ethyl acetate, for 0.5-10 hours at a temperature from -50° C. to 50° C. The obtained compound having the formula (VII) rearranges comparatively easily into the thio urea derivative having the formula ##STR20## when heated in the solvent.

Because of such unstability, it is desirable to be subjected to the following reaction without isolation.

Ring formation is carried out by using oxidizing agent in an organic solvent. As the organic solvent, a general inert solvent such as methylene dichloride, chloroform, N,N-dimethylformamide, ethyl acetate can be used.

At the condensation reaction of ring formation, acid binder(s) may be effectively used according to the kind of oxidizing agent. As the acid binder, an organic base such as triethylamine, pyridine, dimethyl aniline, or an inorganic base such as caustic soda, sodium carbonate, can be use. As the oxidizing agent, bromine, chlorine, sodium hypochlorite or the like are used. In case at least one of R being hydroxy, iodine is preberable as the oxidizing agent.

The compound having the formula (IV)' thus produced may be obtained by a usual procedure of separation and then purified by a conventional purifying procedure such as recrystallization, column chromatography etc.

2. in case Y being oxygen: ##STR21##

The reaction is carried out in the presence of organic or inorganic base in an inert solvent for one (1) to several tens of hours at a temperature from -20° C. to 50° C. As the base, triethylamine, pyridine, sodium carbonate etc. can be used, and as the solvent, methylene dichoride, chloroform etc. can be used.

The compound having the formula (IV)" thus produced may be obtained by a usual procedure of separation and then purified by a conventional purifying procedure such as recrystallization, column chromatography etc.

3. in case Y being sulfur: ##STR22## The reaction is carried out in the presence of organic or inorganic base in an inert solvent for one (1) to 10 hours at a temperature from -20° C. to 50° C. As the base, triethylamine, sodium carbonate, etc. can be used, and as the solvent methylene dichloride, chloroform, etc. can be used. The compound obtained having the formula (IV)'" thus produced may be obtained by a usual procedure of separation and then purified by a conventional purifying procedure such as recrystallization, column chromatography, etc.

The starting material having the formula (XII) can be prepared by chlorination of the corresponding isothiocyanate, and normally, the obtained compound is used to the following reaction without being isolated.

4. in case Y or E being SO, the compound is obtained by oxidation of the corresponding sulfur compound.

And the present compound is also obtainable by the following equation: ##STR23##

Further, owing to the difference of substituent(s) shown by --(R)n, a proper reaction is selected from following equations to prepare the compounds of this invention:

a. in case --GR¹ type (R¹ is not hydrogen): ##STR24##

b. in case ##STR25## type (R² is not hydrogen): ##STR26##

c. in case --NH₂ type (G: nitrogen, and r¹⁰ and R¹ : hydrogen): ##STR27##

d. in case --SR¹ type (--G: S): ##STR28##

e. in case ##STR29## type: ##STR30##

e'. in case ##STR31## type (R is not hydrogen): ##STR32##

f. in case ##STR33## the compound is obtainable by similar reaction to the above.

The chemical structure of the compound obtained was determined by means of NMR spectrum, Mass spectrum and IR spectrum.

The following Examples illustrate the invention.

EXAMPLE 1 3-(5-acetonyloxy-4-chloro-2-fluorophenylimino)-5,6-dihydro-6,6-dimethyl-3H-thiazolo(2,3-C)(1,2,4)thiadiazole (Compound No. 232) ##STR34##

1.5 g of 2-amino-5,5-dimethyl-2-thiazoline was dissolved in 15 ml of methylene dichloride. To this was then added dropwise, under stirring at 0° C., a solution of 3.0 g of 2-fluoro-4-chloro-5-acetonyloxyphenylisothiocyanate in 15 ml of methylene dichloride. After it was then stirred for one hour, the reaction solution was fed with 0.72 g pyridine, and while being ice-cooled, to the solution was added dropwise a solution of 1.7 g of bromine in 10 ml of methylene dichloride. The reaction solution was further stirred for 30 minutes, at the end of which the solution was washed with 30 ml of water, with 30 ml of 5% NaOH solution, and with 30 ml of water, in the order given. The methylene dichloride layer was dried over anhydrous magnesium sulfate. The same layer was filtered and then concentrated. The residue was purified by silica gel column chromatography to give 2.5 g of the objective product. (m.p. 107°-108° C.)

EXAMPLE 2 3-((4-chloro-2-fluoro-5-(1-ethoxycarbonylethoxy)phenylimino))-5,6-dihydro-6-methyl-3H-oxazolo(2,3-C)(1,2,4)thiadiazole (Compound No. 359) ##STR35##

9.60 g of 4-chloro-2-fluoro-5-(1-ethoxycarbonylethoxy)phenyl isothiocyanate was dissolved in 100 ml of chloroform. The solution was then cooled to -10° C. and was fed with 3.80 g of 5-methyl-2-amino-2-oxazoline. The reaction solution was stirred for five hours at 0° C., and then a solution of 5.06 g of bromine in 30 ml of chloroform was added dropwise at -10°-0° C. After the dropwise addition ended, the reaction solution was washed with a 50 ml aqueous solution of 1N-NaOH, then with 50 ml water, and was dried over anhydrous magnesium sulfate. After magnesium sulfate was filtered off, chloroform was removed in vacuo. The residue obtained was purified by column chromatography to give 10.04 g of objective product. (n_(D) ²⁶ 1.5870)

EXAMPLE 3 3-(4-chloro-5-(1-cyanoethoxy)-2-fluorophenylimino)-6,7-dihydro-6-methyl-3H,5H-pyrrolo(2,1-C)(1,2,4)thiadiazole (Compound No. 587 ) ##STR36##

3.25 g of 2-amino-4-methyl-1-pyrroline hydrochloride was suspended to 20 ml of chloroform. While it was ice-cooled, to the suspension was add dropwise a solution of 1 g of caustic soda in 60 ml of water. After 10 minutes of stirring, the reaction mixture, while it was ice-cooled, was further fed dropwise with a solution of 5.6 g of 2-fluoro-4-chloro-5-(1-cyanoethoxy)phenylisothiocyanate in 20 ml of chloroform. After stirring it for three hours at room temperature, the reaction solution was fed dropwise with a solution of 3.15 g of bromine in 10 ml of chloroform under ice-cooling. After stirring at room temperature for one hour, the reaction solution was washed with 30 ml of water. The chloroform layer was dried over anhydrous magnesium sulfate and was then filtered. The filtrate was concentrated and the residue was purified by silica gel column chromatography to give 5.0 g of the objective product. (m.p. 93°-95° C.)

EXAMPLE 4 3-(4-chloro-5-(1-ethoxycarbonylethoxy)-2-fluorophenylimino)-5,6-dihydro-7-methyl-3H-imidazo(2,1-C)(1,2,4)thiadiazole (Compound No. 675) ##STR37##

1.56 g of 2-amino-3-methyl-1-imidazoline hydrobromide was suspended in 10 ml of chloroform. To this suspension was then added dropwise, under ice-cooled conditions, a solution of 0.37 g of caustic soda in 2 ml of water. After cooling it down to -15° C., the reaction solution was fed dropwise with a solution of 2.31 g of 2-fluoro-4-chloro-5-(1-ethoxycarbonylethoxy)phenylisothiocyanate in 10 ml of chloroform. After stirring it for one hour at -15° C., the reaction solution was again fed dropwise with a solution of 1.2 g of bromine in 10 ml of chloroform. After another hour of stirring the reaction solution was washed with 30 ml of water and the chloroform layer was dried over anhydrous magnesium sulfate before it was concentrated. The residue obtained was purified by silica gel column chromatography to give 1.48 g of the objective product. (m.p. 75°-78° C.)

EXAMPLE 5 3-(4-chloro-2 -fluoro-5-isopropoxyphenylimino)-5,6-dihydro-6,6-dimethyl-3H-thiazolo(2,3-C)(1,2,4)oxadiazole (Compound No. 129) ##STR38##

To a solution of 5,5-dimethyl-2-hydroxyiminothiazolidine (1.5 g) and triethylamine (3 g) in chloroform (30 ml) was added dropwise a solution of 4-chloro-2-fluoro-5-isopropoxyphenylisocyanide dichloride (2.8 g) in chloroform (10 ml) at 5°-10° C., and the mixture was stirred at room temperature overnight. The reaction mixture was washed with water, dried over anhydrous magnesium sulfate. Chloroform was removed in vacuo, and the residue was purified by silica gel column chromatography to give 0.8 g of the objective product.

(n_(D) ²⁰ 1.5760)

EXAMPLE 6 3-(4-chloro-5-(1-ethoxycarbonyl ethoxy)-2-fluorophenylimino)-5,6,7,8-tetrahydro-(1,2,4)thiadiazole-(4,3-a)pyridine (Compound No. 679) ##STR39##

The solution of 4-chloro-5-(1-ethoxycarbonylethoxy)-2-fluoro phenyl isothiocyanate (2.0 g) in carbon tetrachloride (10 ml) was added dropwise at 0° C. with stirring to chlorine (0.9 g) in carbon tetrachloride (25 ml).

After stirring at room temperature for 16 hours, the reaction mixture was concentrated under a reduced pressure.

The residue was dissolved in chloroform, and 2-amino-3,4,5,6-tetrahydropyridine (0.51 g) and triethylamine (1.10 g) was added and stirred at 0° C. for 2 hours.

Water was added, and the mixture was extracted with chloroform, dried over anhydrous magnesium sulfate, and concentrated.

The residue was purified by silica gel column chromatography (hexane-ethyl acetate 2:1) to give 0.18 g of the objective product. (m.p. 79°-80.5° C.)

EXAMPLE 7 3-(4-chloro-2-fluoro-5-(0,0-dimethylthio phosphoryloxy)phenylimino)-5,6-dihydro-6-methyl-3H-oxazolo(2,3-C)(1,2,4)thiadiazole (compound No. 518) ##STR40##

0.6 g of 3-(4-chloro-2-fluoro-5-hydroxyphenylimino)-5,6-dihydro-6-methyl-3H-oxazolo(2,3-C)(1,2,4)thiadiazole and 0.27 g of anhydrous potassium carbonate were added to 40 ml of acetone. At room temperature, the reaction solution was fed dropwise with 0.32 g of 0,0-dimethylthiophosphoryl chloride. The solution was heated under reflux for four hours, and was then cooled, thereupon solid matter was filtered off and the filtrate was concentrated under reduced pressure. The residue was purified by column chromatography to give 0.3 g of the objective product. (m.p. 77°-80° C.)

EXAMPLE 8 3-(4-chloro-2-fluoro-5-(1-ethylthiocarbonylethoxy)phenylimino)-5,6-dihydro-6-methyl-3H-oxazolo(2,3-C)(1,2,4)thiadiazole (Compound No. 410) ##STR41##

1.00 g of 3-(4-chloro-2-fluoro-5-(1-carboxyethoxy)phenylimino)-5,6-dihydro-6-methyl-3H-oxazolo(2,3-C)(1,2,4)thiadiazole was dissolved in 30 ml of chloroform. Under stirring at -10° C., the solution was fed with 0.30 g of triethylamine and 0.3 g of methyl chlorocarbonate. After five minutes elapsed, the solution was further fed with 0.20 g of ethyl mercaptan and was stirred for three hours at 0° C. The reaction solution was poured into 50 ml dilute hydrochloric acid to separate the chloroform layer out. The chloroform layer was washed with 30 ml of 1N-NaOH, then with 30 ml of water, and was dried over anhydrous magnesium sulfate. When this was accomplished, magnesium sulfate was filtered off, and the filtrate was concentrated. The residue was purified by column chromatography and the objective product was obtained as an oil in an amount of 0.5 g.

(n_(D) ²⁶ 1.6080)

EXAMPLE 9 3-(4-chloro-2-fluoro-5-(2-hydroxyimino-propoxy)phenylimino)-5,6-dihydro-6,6-dimethyl-3H-thiazolo(2,3-C)(1,2,4)thiadiazole (Compound No. 191) ##STR42##

0.9 g of 3-(5-acetonyloxy-4-chloro-2-fluorophenylimino)-5,6-dihydro-6,6-dimethyl-3H-thiazolo(2,3-C)(1,2,4)thiadiazole and 0.25 g of hydroxyamine hydrochloride were dissolved in 10 ml of ethanol. The solution obtained was fed dropwise under stirring at room temperature with a solution of 0.14 g of caustic soda in 10 ml of water. After one hour of stirring at room temperature, the reaction solution was poured into 60 ml of water and the crystals that precipitated were filtered and washed with water to give 0.8 g of the objective product. (m.p. 152°-156° C.)

EXAMPLE 10 3-(4-chloro-5-fluoro-5-(1-(1-phenyl-2-propynyloxycarbonyl)ethoxy phenylimino)-6,7-dihydro-6-methyl-3H,5-pyrrolo(2,1-C)(1,2,4)thiadiazole (Compound No. 610) ##STR43##

1.00 g of 3-(4-chloro-2-fluoro-5-(1-carboxyethoxy)phenylimino)-6,7-dihydro-6-methyl-3H,5H-pyrrolo(2,1-C)(1,2,4)thiadiazole was added to 10 ml of benzene, to which were then added under stirring at room temperature 0.83 g of thionyl chloride and a drop of pyridine. 20 hours of heating under reflux produced a corresponding acid chloride. The low-boiling component was distilled off under reduced pressure. The residue was again fed with 10 ml of benzene, and further at room temperature with 0.73 g of 1-phenyl-2-propyne-1-ol and with 0.44 g of pyridine, and was stirred for four hours. The reaction solution was poured into water to separate the benzene layer. The water layer was extracted with 30 ml of ethyl acetate. The organic layer, was combined, washed with 20 ml of 5% hydrochloric acid water, with 20 ml of 5% sodium hydrogen carbonate, and with 20 ml of saline solution in this order. After it was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure and the residue was purified by column chromatography to give 0.4 g of the objective product.

(n_(D) ²¹ 1.5957)

EXAMPLE 11 3-(4-chloro-5-(1-thiocarbamoylethoxy)-2-fluorophenylimino)-6-6,7-dihydro-6-methyl-3H,5H-pyrrolo(2,1-C)(1,2,4)thiadiazole (Compound No. 614) ##STR44##

1 g of 3-(4-chloro-5-(1-cyanoethoxy)-2-fluorophenylimino)-6,7-dihydro-6-methyl-3H,5H-pyrrolo(2,1-C)(1,2,4)thiadiazole and 0.3 g of triethylamine were dissolved in 2 ml of pyridine. To the solution, while it was ice-cooled, was gradually introduced hydrogen sulfide. The reaction mixture was TLC-analyzed with the progress of time and the reaction stopped as soon as raw material spot disappeared. The reaction liquid was fed with 10 ml of ethyl acetate and was washed with dilute hydrochloric acid. The ethylacetate layer was rinsed, dried over anhydrous magnesium sulfate filtered, and, concentrated under reduced pressure. The residue was purified by silicagel column chromatography to give 0.5 g of the objective product. (m.p. 134.5°-135° C.)

EXAMPLE 12 3-(4-chloro-5-(1-(N-chloroacetoxyamidino)ethoxy)-2-fluorophenylimino)-6,7-dihydro-6-methyl-3H,5H-pyrrolo(2,1-C)(1,2,4)thiadiazole (Compound No. 577) ##STR45##

1 g of 3-(4-chloro-5-(1-cyanoethoxy)-2-fluorophenylimino)-6,7-dihydro-methyl-3H,5H-pyrrolo(2,1-C)(1,2,4)thiadiazole was dissolved in ethanol, to which was then added dropwise under stirring at room temperature a solution of 0.23 g hydroxylamine hydrochloride and 0.23 g anhydrous potassium carbonate in 3 ml of water. This reaction mixture was heated under reflux for two hours, at the end of which it was poured into ice-cooled water. The crystals that precipitated out were filtered, rinsed, and then dried, and 0.9 g of crude amidoxime was obtained. 0.9 g of crude amidoxime and 0.25 g of triethylamine were dissolved in 10 ml of THF, to which was then added dropwise, under ice-cooled conditions, a solution of 0.27 g of chloroacetyl chloride in 5 ml of THF. After it was stirred for one hour at 50° C., the reaction solution was charged with 40 ml of water and 40 ml of chloroform. The chloroform layer was dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue obtained was then recrystallized from benzene to give 0.4 g of the objective product. (d.p. 128°-129° C.)

EXAMPLE 13 3-(5-carboxy-4-chloro-2-fluorophenylimino)-6,7-dihydro-6-methyl-3H,5H-pyrrolo(2,1-C)(1,2,4)thiadiazole (Compound No. 561) ##STR46##

To a solution of 3-(4-chloro-2-fluoro-5-ethoxycarboxylphenylimino)-6,7-dihydro-6-methyl-3H,5H-pyrrolo(2,1-C)(1,2,4)thiadiazole (8.5 g) in tetrahydrofuran (60 ml) and methanol (30 ml) was added a aqueous solution (50 ml) of sodium hydroxide (2.9 g) at room temperature, and the mixture was stirred at 50° C. for 0.5 hour. The reaction mixture was acidified with 1N hydrochloric acid, and concentrated to half volume. The residue was extracted with ethylacetate, washed with water, dried over anhydrous magnesium sulfate, and concentrated. The residue was crystallized from ether-n-hexane to give 7.5 g of the objective compound. (m.p. 210°-213° C.)

EXAMPLE 14 3-(4-chloro-5-(1-ethoxycarbonylethoxycarbonyl)-2-fluorophenylimino)-6,7-dihydro-6-methyl-3H,5H-pyrrolo(2,1-C)(1,2,4)thiadiazole (Compound No. 683) ##STR47##

To a solution of 3-(5-carboxy-4-chloro-2-fluorophenylimino)-6,7-dihydro-6-methyl-3H,5H-pyrrolo(2,1-C)(1,2,4)thiadiazole (0.7 g) in acetonitrile (10 ml), there were added anhydrous potassium carbonate (0.3 g) and 2-bromopropionic acid ethyl ester (0.4 g) and the mixture was heated at reflux for 4 hours. After being allowed to cool to room temperature, the reaction mixture was filtered, and the filtrate was concentrated under reduced pressure. The residue was recrystallized from ether-hexane to give 0.8 g of the objective product. (m.p. 83°-84° C.)

EXAMPLE 15 3-(4-chloro-2-fluoro-5-tert-butoxycarbonyl phenylimino)-6,7-dihydro-6-methyl-3H,5H-pyrrolo(2,1-C)(1,2,4)thiadiazole (Compound No. 537) ##STR48##

To a solution of 3-(5-carboxy-4-chloro-2-fluorophenylimino)-6,7-dihydro-6-methyl-3H,5H-pyrrolo(2,1-C)(1,2,4)thiadiazole (3 g) in benzene (20 ml), there was added thionyl chloride 3.3 g), and the mixture was heated at reflux for 0.5 hour. The reaction mixture was concentrated under reduced pressure, the residue, which was dissolved in benzene (20 ml), was dropwise added to the suspension of potassium test-butoxide (2.1 g) in benzene (20 ml) at 5°-10° C. After stirring at room temperature for 2 hours, cold water was added to this reaction mixture. The benzene layer was washed with water, and dried over anhydrous magnesium sulfate. Benzene was removed in vacuo, and the residue was recrystallized from ether-n-hexane to give 1.5 g of the objective product. (m.p. 89°-90° C.)

EXAMPLE 16 3-(4-chloro-2-fluoro-5-(2-propynylamino)phenylimino)-5,6-dihydro-6,6-dimethyl-3H-thiazolo(2,3-C)(1,2,4)thiadiazole (Compound No. 108) ##STR49##

To 3-(5-amino-4-chloro-2-fluorophenylimino)-5,6-dihydro-6,6-dimethyl-3H-thiazolo-(2,3-C)(1,2,4)thiadiazole (1.69 g) in ethanol (20 ml) was added anhydrous sodium carbonate (0.82 g) and 2-propynyl bromide (0.77 g).

The resultant mixture was refluxed for 19 hours. After being allowed to cool, water was added, and the mixture was extracted with chloroform, dried over anhydrous magnesium sulfate, and concentrated.

The residue was purified by silicagel column chromatography (benzenechloroform 2:1) to give 1.17 g of the objective product. (m.p. 117°-117.5° C.)

EXAMPLE 17 3-(5-amino-4-chloro-2-fluorophenylimino)-5,6-dihydro-6,6-dimethyl-3H-thiazolo-(2,3-C)(1,2,4)thiadiazole (Compound No. 105) ##STR50##

3-(4-chloro-2-fluoro-5-nitrophenylimino)-5,6-dihydro-6,6-dimethyl-3H-thiazolo-(2,3-C)(1,2,4)thiadiazole (5.28 g) was dissolved in methyl ethyl ketone (40 ml), and acetic acid (1.96 g), iron powder (3.86 g), water (20 ml) was added.

The resultant mixture was stirred at room temperature for 30 minutes, and 70° C. for 1.5 hours. After being allowed to cool 20% aqueous sodium hydroxide (20 ml) and ethyl acetate (40 ml) was added to the resultant mixture, followed by filtration on celite.

The organic layer was separated and the aqueous layer was extracted with chloroform, and the extracts were combined, dried over anhydrous magnesium sulfate and concentrated.

The residue was purified by silicagel solumn chromatography (benzene-CHCl₃ 1:6) to give 2.02 g of the objective product. (m.p. 141°-142° C.)

EXAMPLE 18 3-(4-chloro-2-fluoro-5-carboxymethylthiophenylimino)-6,7-dihydro-6-methyl-3H,5H-pyrrolo (2,1-C)(1,2,4)thiadiazole (Compound No. 740) ##STR51##

To the solution of 2.0 g of 3-(4-chloro-2-fluoro-5-aminophenylimino-6,7-dihydro-6-methyl-3H,5H-pyrrolo(2,1-C)(1,2,4)thiadiazole in 5 ml of concentrated sulfuric acid and 50 ml of water was added 0.56 g of sodium nitrate in 5 ml of water at -5°-0° C. The reaction mixture was stirred for 30 minutes, then 0.1 g of urea was added to destroy excess sodium nitrite. 0.8 g of thiogycolic acid and 0.5 g of cupric carbonate in 10 ml of water was added to the reaction mixture at room temperature and stirred for one hour. The reaction mixture was extracted with ethyl acetate, organic layer was washed with water, dried over anhydrous magnesium sulfate and concentrated.

The residue was purified by silicagel column chromatography to obtain 0.5 g of the objective compound.

EXAMPLE 19 3-(4-chloro-2-fluoro-5-isopropoxycarbonylmethylthiophenylimino)-6-methyl-5,6,7,7a-tetrahydro-3H-pyrrolo(2,1-C)(1,2,4)thiadiazole (Compound No. 707) ##STR52##

0.4 g of 3-(4-chloro-2-fluoro-5-carboxymethylthiophenylimino)-6-methyl-5,6,7,7a-tetrahydro-3H-pyrrolo(2,1-C)(1,2,4)thiadiazole, 0.22 g of isopropyl iodide, 0.15 g of anhydrous potassium carbonate and 10 ml of acetonitrile were mixed together and heated to reflux for 3 hours. After being allowed to cool the precipitate was filtered off. The filtrate was concentrated under reduced pressure. The residue was purified by silicagel column chromatography to obtain 0.2 g of the objective product. (m.p. 79°-82° C.)

EXAMPLE 20 Oxidation of 3-(4-chlorophenylimino)-6,6-dimethyl-5,6-dihydro-3H-thiazolo(2,3-C)(1,2,4)thiadiazole (Compound No. 36 and 81) ##STR53##

To a solution of 3-(4-chlorophenylimino)-6,6-dimethyl-5,6-dihydro-3H-thiazolo(2,3-C)(1,2,4)thiadiazole (2.2 g) in dichloromethane (20 ml) was added a solution of m-chloroperbenzoic acid (3.0 g) in dichloromethane (20 ml) at room temperature. After stirring for 2 hours at room temperature, the reaction mixture was filtered. The filtrate was washed with 10% aqueous sodium hydroxide solution, dried over anhydrous magnesium sulfate and concentrated.

The residue was purified by silicagel column chromatography to obtain 0.6 g of 3-(4-chlorophenylimino)-6,6-dimethyl-5,6-dihydro-3H-thiazolo(2,3-C)(1,2,4)thiadiazole-2-oxide (m.p. 121°-124° C.) and 0.6 g of 3-(4-chlorophenylimino)-6,6-dimethyl-5,6-dihydro-3H-thiazolo(2,3-C)(1,2,4)thiadiazole-7-oxide. (m.p. 115°-120° C.)

Inclusive the above, each compound within the scope of this invention which can be prepared in analogous method(s) is tabulated in Table 1.

                                      TABLE 1                                      __________________________________________________________________________      poundCom-                                                                          ##STR54##                                           PropertiesPhysica                                                             l                      No. X       Y   r.sup.1, r.sup.2, r.sup.3, r.sup.4                                                         (R)n                        m.p.                   __________________________________________________________________________                                                             °C.             1   S       S   6,6-(CH.sub.3).sub.2                                                                       5-CF.sub.3                  71-72                  2   "       "   "           4-Cl, 5-CF.sub.3            103-104                3   "       "   "           2-F, 4-Cl, 5-CH.sub.2 Cl    89-90                  4   "       "   "           2-F, 4-Cl, 5-CH.sub.2 OCH.sub.3                                                                            80-83                  5   "       "   "           2-F, 4-Cl, 5-CH.sub.2 OCOCH.sub.3                                                                          96-97                  6   "       "   "           2-F, 4-Cl, 5-CH.sub.2 OH    169-170                7   "       "   "           2-F, 4-Cl, 5-CHCHCOOC.sub.2 H.sub.5                                                                        89-91                  8   "       "   "           2-F, 4-Cl, 5-CHNOC.sub.2 H.sub.5                                                                           n.sub.D.sup.22.5                                                               1.6334                 9   "       "   "           2-F, 4-Cl, 5-CHNOCH.sub.2 COOC.sub.2 H.sub.5                                                               113-114                10  "       "   "           2-F, 4-Cl, 5-COOC.sub.2 H.sub.4 OCH.sub.3                                                                  105-107                11  "       "   "           2-F, 4-Cl, 5-COOC.sub.2 H.sub.5                                                                            108-109                12  "       "   "           4-Cl, 5-COOC.sub.2 H.sub.5  74-77                  13  "       "   "           2-F, 4-Cl, 5-COO.sup.i C.sub.3 H.sub.7                                                                     76-78                  14  "       "   "           2-F, 4-Cl, 5-COOCH.sub.2 CCH                                                                               102-103                15  "       "   "           2-F, 4-Cl, 5-COOCH.sub.2 COOC.sub.2 H.sub.5                                                                n.sub.D.sup.27                                                                 1.5938                 16  "       "   "           2-F, 4-Cl, 5-COOCH.sub.3    106-107                17  "       "   "           2-F, 4-Cl, 5-COOH           239-242                18  "       "   "           4-Cl, 5-COOH                221-223                19  "       "   --          4,5-Cl.sub.2                115- 117               20  "       "   --          3,5-Cl.sub.2                89-91                  21  "       "   6,6-(CH.sub.3).sub.2                                                                       3,5-Cl.sub.2                145-147                22  "       "   "           5-Cl                        68-70                  23  "       "   "           4,5-Cl.sub.2                109-110                24  "       "   "           3,5-Cl.sub.2, 4-OC.sub.2 H.sub.5                                                                           n.sub.D.sup.17.5                                                               1.6301                 25  "       "   "           2,4-F.sub.2, 5-Cl             103-103.5            26  "       "   "           2,3,4,5,6-F.sub.5           113.5-115              27  "       "   "           2,5-F.sub.2, 4-Br           127-128                28  "       "   "           2,4,5-F.sub.3               111-112                29  "       "   "           2,5-F.sub.2, 4-Cl           133-134                30  "       "   --          4-Cl                        114-115                31  "       "   --          4-CH.sub.3                  102-104                32  "       "   --          2,4-Cl.sub.2                137-139                33  "       "   --          4-NO.sub.2                  178-179                34  "       "   --          4-Br                        138-140                35  "       "   --          2-Cl, 4-F                     103-104.5            36                                                                                  ##STR55##                                                                             "   6,6-(CH.sub.3).sub.2                                                                       4-Cl                        115-120                37  S       "   6-CH.sub.3  4-Cl                        118-122                38  "       "   "           4-Cl (HBr salt)             167-170                39  "       "   "           2-F, 4-Cl                   78-80                  40  "       "   6,6-(CH.sub.3).sub.2                                                                       4-Cl                        92-94                  41  "       "   "           4-Br                        118-120                42  "       "   "           4-CF.sub.3                  112-113                43  "       "   "           4-C.sub.3 H.sub.7           56-57                  44  "       "   "           2,4-Cl.sub.2                80-82                  45  "       "   "           2-Cl                        74-75                  46  "       "   "                                                                                           ##STR56##                  116-118                47  "       "   "           4-F                         88-90                  48  "       "   "           2-CF.sub.3, 4-Cl            106-108                49  "       "   6-CH.sub.3, 6-C.sub.2 H.sub.5                                                              4-Cl                        70-71                  50  "       "   6-CH.sub.3, 6-C.sub.3 H.sub.7                                                              4-Cl                        162 dec.               51  "       "   6,6-(CH.sub.3).sub.2                                                                       4-OCF.sub.3                 70-71                  52  "       "   "           2-CH.sub.3, 4-Cl            82-83                  53  "       "   "           2-F, 4-Cl                   100-102                54  "       "   "           2,4-F.sub.2                 110-111                55  "       "   "           2-OCH.sub.3, 4-Cl           137-138                56  "       "   "           4-COOC.sub.2 H.sub.5        124-125                57  "       "   "           4-Cl (HBr salt)             220-221 dec.           58  "       "   "           4-NO.sub.2                  153.5-154.5            59  "       "   "           2,4,6-Cl.sub.3              138-139                60  "       "   "           2-F, 4-Br                   98-99                  61  "       "   "                                                                                           ##STR57##                  178-179                62  "       "   "           4-Cl (CH.sub.3 SO.sub.3 H salt)                                                                            136-138                63  "       "   "           4-Cl ((COOH).sub.2 salt)    121-122                64  "       "   "           2-Cl, 4-F                   102-103                65  "       "   "           2,6-F.sub.2                 91-92                  66  "       "   "           2,4,6-F.sub.3               86-87                  67  "       "   "           2,6-F.sub.2, 4-Br           103-104                68  "       "   "           4-CH.sub.3                  87-88                  69  "       "   "           2-Br, 4-CH.sub.3            130-131                70  "       "   "           2-Br, 4-F                   90-91                  71  "       "   "           4-OCH.sub.3                 77-79                  72  "       "   "           2-Br, 4-NO.sub.2            151-153                73  "       "   "           2-CH.sub.3, 4-Cl            77-79                  74  "       "   "           2,3-F.sub.2, 4-Br           156-157                75  "       "   "           2-F, 4-OCH.sub.3            105-107                76  "       "   "           2-OCH.sub.3, 4-F            n.sub.D.sup.26.5                                                               1.6069                 77  "       "   "           2-F, 4-OCH.sub.2 CCH        n.sub.D.sup.25                                                                 1.6269                 78  "       "   "                                                                                           ##STR58##                  134-135                79  "       "   "                                                                                           ##STR59##                  n.sub.D.sup.25                                                                 1.5774                 80  "       "   "           3-Cl, 4-F                   72-76                  81  "                                                                                       ##STR60##                                                                         "           4-Cl                        121-124                82  "       S                                                                                   ##STR61##  4-Cl                        105-108                83  "       "   6-CH.sub.2 SCH.sub.3                                                                       4-Cl                        109.5-110.5            84  "       "   6-iC.sub.3 H.sub.7                                                                         4-Cl                        76.5-79                85  "       "   "           2,4-Cl.sub.2                112-113                86  "       "   6-C.sub.2 H.sub.5                                                                          4-Cl                        104-107                87  "       "   "           2,4-Cl.sub.2                127-129                88  "       "   "           2,4-F.sub.2                 98-99                  89  "       "   "           4-I                         103-106                90  "       "   "           4-Br                        104-105                91  "       "   "           2-F, 4-Cl                   91-92                  92  "       "   "           2-F, 4-Br                   66-67                  93  "       "   6-C.sub.3 H.sub.7                                                                          4-Cl                        84-85                  94  "       "   6-C.sub.4 H.sub.9                                                                          4-Cl                        n.sub.D.sup.31                                                                 1.6425                 95  "       "                                                                                   ##STR62##  4-Cl                         124-125               96  "       "                                                                                   ##STR63##  2-Cl, 4-F                   126-129                97  "       "   "           4-Cl                        111-112                98  "       "                                                                                   ##STR64##  4-Cl                        107-109                99  "       "                                                                                   ##STR65##  4-Cl                        107-110                100 "       "   5-CH.sub.3, (trans)                                                                        2-Cl, 4-F                   78-82                  101 "       "   6-iC.sub.3 H.sub.7                                                                         4-Cl                        114-116                102 "       "   6,6-(CH.sub.3).sub.2                                                                       2-F, 4-Cl, 5-N(CH.sub.2 CCH).sub.2                                                                           141-141.5            103 "       "   "                                                                                           ##STR66##                  146.5-147.5            104 "       "   "                                                                                           ##STR67##                  94-97                  105 "       "   "           2-F, 4-Cl, 5-NH.sub.2       141-142                106 "       "   "                                                                                           ##STR68##                  n.sub.D.sup.28.5                                                               1.5981                 107 "       "   "           2-F, 4-Cl, 5-NHCH.sub.2 COOCH.sub.2 CHClCH.sub                                 .2 Cl                       n.sub.D.sup.25                                                                 1.6031                 108 "       "   "           2-F, 4-Cl, 5-NHCH.sub.2 CCH   117-117.5            109 "       "   "           2-F, 4-Cl, 5-NHCOC.sub.2 H.sub.5                                                                           170.5-174              110 "       "   "           2-F, 4-Cl, 5-NHCOOCH.sub.3  111-114                111 "       "   "           2-F, 4-Cl, 5-NO.sub.2       161.5-162              112 "       "   "                                                                                           ##STR69##                  134-135                113 "       "   "                                                                                           ##STR70##                  50-51                  114 "       "   "                                                                                           ##STR71##                  250° C.                                                                 up                     115 "       "   "           2-F, 4-Cl, 5-OC.sub.2 H.sub.5                                                                              104-107                116 "       "   "           2,4-Cl.sub.2, 5-OiCH.sub.3 H.sub.7                                                                         125-129                117 "       "   "           2-F, 4-Br, 5-OiC.sub.3 H.sub.7                                                                             105-107                118 "       "   "           2-F, 4-Cl, 5-OiC.sub.3 H.sub.7                                                                             n.sub.D.sup.21                                                                 1.6084                 119 "       "   "           2-F, 4-Cl, 5-OC.sub.3 H.sub.7                                                                              85-87                  120 "       "   "           2-F, 4-Cl, 5-OC.sub.4 H.sub.9                                                                              58-60                  121 "       "   "           2,4-Cl.sub.2, 5-OCF.sub.2 HCF.sub.2 H                                                                      104-106                122 "       "   "                                                                                           ##STR72##                  82-84                  123 "       "   "                                                                                           ##STR73##                  n.sub.D.sup.27                                                                 1.5975                 124 "       "   "                                                                                           ##STR74##                  n.sub.D.sup.24                                                                 1.5881                 125 "       "   "                                                                                           ##STR75##                  80-82                  126 "       "   "                                                                                           ##STR76##                  n.sub.D.sup.28                                                                 1.5932                 127 "       "   "                                                                                           ##STR77##                  95-96                  128 "       "   "                                                                                           ##STR78##                  n.sub.D.sup.28                                                                 1.5790                 129 "       O   "           2-F, 4-Cl, 5-O.sup.i C.sub.3 H.sub.7                                                                       n.sub.D.sup.20                                                                 1.5760                 130 "       S   "                                                                                           ##STR79##                  n.sub.D.sup.26.5                                                               1.6093                 131 "       "   "                                                                                           ##STR80##                  151-153                132 "       "   "                                                                                           ##STR81##                  55-57                  133 "       "   "                                                                                           ##STR82##                  n.sub.D.sup.28.5                                                               1.6093                 134 "       "   "                                                                                           ##STR83##                  n.sub.D.sup.22                                                                 1.6020                 135 "       "   "                                                                                           ##STR84##                  n.sub.D.sup.24                                                                 1.6091                 136 "       "   "                                                                                           ##STR85##                  n.sub.D.sup.28                                                                 1.5798                 137 "       "   "                                                                                           ##STR86##                  n.sub.D.sup.28                                                                 1.6092                 138 "       "   "                                                                                           ##STR87##                  96-99                  139 "       "   "                                                                                           ##STR88##                  93-94                  140 "       "   "                                                                                           ##STR89##                  152-154                141 "       "   "                                                                                           ##STR90##                  102-104                142 "       "   "                                                                                           ##STR91##                  110-112                143 "       "   "                                                                                           ##STR92##                  84-87                  144 "       "   "                                                                                           ##STR93##                  n.sub.D.sup.27                                                                 1.5739                 145 "       "   "                                                                                           ##STR94##                  117-120                146 "       "   6-CH.sub.3                                                                                  ##STR95##                  158-160                147 "       "   6,6-(CH.sub.3).sub.2                                                                        ##STR96##                  145-146                148 "       "   "                                                                                           ##STR97##                  52-54                  149 "       "   "                                                                                           ##STR98##                  90-93                  150 "       "   "                                                                                           ##STR99##                  n.sub.D.sup.23                                                                 1.5912                 151 "       "   "                                                                                           ##STR100##                 n.sub.D.sup.22.5                                                               1.5870                 152 "       "   "                                                                                           ##STR101##                 84-85                  153 "       "   "                                                                                           ##STR102##                 103-104                154 "       "   "                                                                                           ##STR103##                 n.sub.D.sup.24.5                                                               1.5545                 155 "       "   --                                                                                          ##STR104##                 84-86                  156 "       "   6-CH.sub.3                                                                                  ##STR105##                 80-83                  157 "       "   6.6-(CH.sub.3).sub.2                                                                        ##STR106##                 n.sub.D.sup. 20.5                                                              1.5998                 158 "       "   "                                                                                           ##STR107##                 n.sub.D.sup.20                                                                 1.5870                 159 "       "   "                                                                                           ##STR108##                 n.sub.D.sup.26.5                                                               1.5988                 160 "       "   "                                                                                           ##STR109##                 n.sub.D.sup.23                                                                 1.5903                 161 "       "   "                                                                                           ##STR110##                 n.sub.D.sup.17.5                                                               1.5843                 162 "       "   "                                                                                           ##STR111##                 n.sub.D.sup.21                                                                 1.5838                 163 "       "   "                                                                                           ##STR112##                 43-44                  164 "       "   "                                                                                           ##STR113##                 n.sub.D.sup.20.5                                                               1.5777                 165 "       "   "                                                                                           ##STR114##                 124-128                166 "       "   "           2-F, (optical isomer)       n.sub.D.sup.27                                                                 1.5670                 167 "       "   --                                                                                          ##STR115##                 111-113                168 "       "   6-CH.sub.3                                                                                  ##STR116##                 81-83                  169 "       "   6,6-(CH.sub.3).sub.2                                                                        ##STR117##                 n.sub.D.sup.24                                                                 1.5971                 170 "       "   "                                                                                           ##STR118##                 n.sub.D.sup.27.5                                                               1.5713                 171 "       "   "                                                                                           ##STR119##                 n.sub.D.sup.24                                                                 1.5784                 172 "       "   "                                                                                           ##STR120##                 50-53                  173 "       "   "                                                                                           ##STR121##                 n.sub.D.sup.26                                                                 1.5941                 174 "       "   "                                                                                           ##STR122##                 n.sub.D.sup.29                                                                 1.5939                 175 "       "   "                                                                                           ##STR123##                 n.sub.D.sup.26                                                                 1.6002                 176 "       "   6-CH.sub.3                                                                                  ##STR124##                 90-92                  177 "       "   6,6-(CH.sub.3).sub.2                                                                        ##STR125##                 n.sub.D.sup.26                                                                 1.5885                 178 "       "   --                                                                                          ##STR126##                 163-165                179 "       "   6-CH.sub.3                                                                                  ##STR127##                 121-123                180 "       "   6,6-(CH.sub.3).sub.2                                                                        ##STR128##                 203-205                181 "       "   "                                                                                           ##STR129##                 164-170                182 "       "   "                                                                                           ##STR130##                 44-46                  183 "       "   "                                                                                           ##STR131##                 n.sub.D.sup.26.5                                                               1.6065                 184 "       "   "                                                                                           ##STR132##                 73-75                  185 "       "   "                                                                                           ##STR133##                 95-97                  186 "       "   6-CH.sub.3  2-F, 4-Cl, 5-OCH(COOC.sub.2 H.sub.5).sub.2                                                                 n.sub.D.sup.29                                                                 1.5830                 187 "       "   6,6-(CH.sub.3).sub.2                                                                       2-F, 4-Cl, OCH(COOC.sub.2 H.sub.5).sub.2                                                                   n.sub.D.sup.27.5                                                               1.5820                 188 "       "   "                                                                                           ##STR134##                 n.sub.D.sup.22                                                                 1.6248                 189 "       "   "                                                                                           ##STR135##                 124-126                190 "       "   6,6-(CH.sub.3).sub.2                                                                        ##STR136##                 n.sub.D.sup.26.5                                                               1.5950                 191 "       "   "                                                                                           ##STR137##                 152-156                192 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 CCCH.sub.3                                                                          98-99                  193 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 CC.Cl                                                                               96-97                  194 "       "   --          2-F, 4-Cl, 5-OCH.sub.2 CCH  116-117                195 "       "   6-CH.sub.3  2-F, 4-Cl, 5-OCH.sub.2 CCH  117-118                196 "       "   6,6-(CH.sub.3).sub.2                                                                       2-F, 4-Br, 5-OCH.sub.2 CCH  114-115                197 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 CCH  103-106                198 "       "   "           2-F, 4,5-(OCH.sub.2 CCH).sub.2                                                                             104-105                199 "       "   "           2,4-F.sub.2, 5-OCH.sub.2 CCH                                                                                99-100                200 "       "   "           2,4-F, 5-OCH.sub.2 CCH, 6-Cl                                                                               106-108                201 "       "   "           2,6-F, 4-Cl, 5-OCH.sub.2 CCH                                                                               n.sub.D.sup.28                                                                 1.6040                 202 "       "   "           2-f, 4-OCH.sub.3, 5-OCH.sub.2 CCH                                                                          124-126                203 "       "   "                                                                                           ##STR138##                 n.sub.D.sup.30                                                                 1.6310                 204 "       "   "           4-Cl, 5-OCH.sub.2 CCH       n.sub.D.sup.23                                                                 1.6388                 205 "       "   6-C.sub.2 H.sub.5                                                                          2-F, 4-Cl, 5-OCH.sub.2 CCH  126-128                206 "       O   6,6-(CH.sub.3).sub.2                                                                       2-F, 4-Cl, 5-OCH.sub.2 CCl.sub.2 CHCl.sub.2                                                                155-157                207 "       S   "           2-F, 4-Cl, 5-OCH.sub.2 CClCH.sub.2                                                                         126-128                208 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 CF.sub.3                                                                            91-92                  209 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 CH.sub.2 OCHCH.sub.2                                                                96-98                  210 "       "   "           2-F, 4-Cl, 5-OC.sub.3 H.sub.6 CN                                                                           91-93                  211 "       "   "           2-F, 4-Cl, 5-OC.sub.3 H.sub.6 COCH.sub.3                                                                   n.sub.D.sup.27                                                                 1.5841                 212 "       "   "           2-F, 4-Cl, 5-OC.sub.3 H.sub.6 COOC.sub.2                                       H.sub.5                     n.sub.D.sup.24                                                                 1.5929                 213 "       "   "           2-F, 4-Cl, 5-OC.sub.2 H.sub.4 OC.sub.2                                         H.sub.4 OCH.sub.3           n.sub.D.sup.23                                                                 1.5880                 214 "       "   "           2-F, 4-Cl, 5-OC.sub.2 H.sub.4 OCH.sub.3                                                                    n.sub.D.sup.21.5                                                               1.6109                 215 "       "   "           2-F, 4-Cl, 5-OC.sub.2 H.sub.4 OCOCH.sub.3                                                                  81-82                  216 "       "   "                                                                                           ##STR139##                 125-127                217 "       "   "                                                                                           ##STR140##                 132-133                218 "       "   "                                                                                           ##STR141##                 137-139                219 "       "   "                                                                                           ##STR142##                 137-138                220 "       "   "           2-F, 4-Cl, 5-OC.sub.2 H.sub.4 SCH.sub.3                                                                    119-121                221 "       "   "           2-F, 4-Cl, 5-OC.sub.2 H.sub.4 SO.sub.2                                         CH.sub.3                    151-154                222 "       "   "           2-F, 4-Cl, 5-OC.sub.2 H.sub.4 SOCH.sub.3                                                                   n.sub.D.sup.26                                                                 1.6141                 223 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 CHCCl.sub.2                                                                          99-102                224 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 CHCH.sub.2                                                                          72-73                  225 "       "   "           2-F, 4-Br, 5-OCH.sub.2 CHCH.sub.2                                                                          n.sub.D.sup.22.5                                                               1.6391                 226 "       "   "           2,4-F.sub.2, 5-OCH.sub.2 CHCH.sub.2                                                                        50-53                  227 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 CHCHCH.sub.3                                                                        65-67                  228 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 CHCHCOOC.sub.2                                                                      n.sub.D.sup.24                                                                 1.5991                 229 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 CHCHCl                                                                              108-109                230 "       "   "           2-F, 4-Br, 5-OCH.sub.2 CN   n.sub.D.sup.33                                                                 1.6257                 231 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 CN   89-90                  232 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 COCH.sub.3                                                                          107-108                233 "       "   "                                                                                           ##STR143##                 133-116                234 "       "   "           2-F, 4-Br, 5-OCH.sub.2 COOC.sub.2 H.sub.5                                                                  105-106                235 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 COOCH.sub.2 CHClCH.sub.                                 2 Cl                        n.sub.D.sup.26                                                                 1.5979                 236 "       "   "                                                                                           ##STR144##                 86-89                  237 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 OC.sub.2 H.sub.5                                                                    54-55                  238 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 OCH.sub.3                                                                           143.5-144              239 "       "   "                                                                                           ##STR145##                 107-109                240 "       "   "                                                                                           ##STR146##                   130-131.5            241 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 SCH.sub.3                                                                           110-114                242 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 SO.sub.2 CH.sub.3                                                                   48-51                  243 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 SOCH.sub.3                                                                          122-124                244 "       "   "                                                                                           ##STR147##                 n.sub.D.sup.28                                                                 1.6514                 245 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 Si(CH.sub.3).sub.3                                                                  n.sub.D.sup.22                                                                 1.5871                 246 "       "   "           2,4-Cl.sub.2, 5-OCH.sub.3   129-130                247 "       "   "           2-F, 4-Cl, 5-OCH.sub.3      131-132                248 "       "   "           2-F, 4-Br, 5-OCH.sub.3      119-121                249 "       "   "           2-F, 4,5-(OCH.sub.3).sub.2  178-179.5              250 "       "   "           2,4-Cl.sub.2, 5-OCH.sub.2 C CH                                                                             124.5-125              251 "       "   "                                                                                           ##STR148##                 n.sub.D.sup.24                                                                 1.5835                 252 "       "   "           2-F, 4-Cl, 5-OCOCH.sub.3    130-131                253 "       "   "           2-F, 4-Cl, 5-OCON(CH.sub.3).sub.2                                                                          140-142                254 "       "   "           2-F, 4-Cl, 5-OCONHC.sub.2 H.sub.5                                                                          136-138                255 "       "   "           2-F, 4-Cl, 5-OH             207-208                256 "       "   "                                                                                           ##STR149##                 n.sub.D.sup.28                                                                 1.5878                 257 "       "   "                                                                                           ##STR150##                 105-108                258 "       "   "                                                                                           ##STR151##                 158-161                259 "       "   "           2-F, 4-Cl, 5-OSO.sub.2 CH.sub.3                                                                            130-131                260 O       "   6-CH.sub.3                                                                                  ##STR152##                 130-132                261 "       "   "           2-F, 4-Cl, 5-CH.sub.2 OCOCH.sub.3                                                                          72-73                  262 "       "   "           2-F, 4-Cl, 5-CHCHCOOC.sub.2 H.sub.5                                                                          115-116.5            263 "       "   "           2-F, 4-CL, 5-CHNOC.sub.2 H.sub.5                                                                            99-102                264 "       "   "           2-F, 4-Cl, 5-CHNOCH.sub.2 COOC.sub.2 H.sub.5                                                               n.sub.D.sup.21.5                                                               1.5720                 265 "       "   "           2-F, 4-Cl, 5-CON(CH.sub.3).sub.2                                                                           170-171                266 "       "   "           2-F, 4-Cl, 5-CONHC.sub.2 H.sub.5                                                                           161-162                267 "       "   "           2-F, 4-Cl, 5-CONH.sup.i C.sub.3 H.sub.7            268 "       "   "           2-F, 4-Cl, 5-CONHCH.sub.2 CCH                                                                              163-165                269 "       "   "           2-F, 4-Cl, 5-CONHOC.sub.2 H.sub.5                                                                            142-143.5            270 "       "   "           2-F, 4-Cl, 5-COOC.sub.2 H.sub.5                                                                            123-124                271 "       "   "           4-Cl, 5-COOC.sub.2 H.sub.5  n.sub.D.sup.23                                                                 1.6006                 272 "       "   "           2-F, 4-Cl, 5-COO.sup.i C.sub.3 H.sub.7                                                                     68-71                  273 "       "   "                                                                                           ##STR153##                 127.5-129              274 "       "   "                                                                                           ##STR154##                 89-91                  275 "       "   "                                                                                           ##STR155##                 112-114                276 "       "   "           2-F, 4-Cl, 5-COOCH.sub.2 CCH                                                                                 132-133.5            277 "       "   "                                                                                           ##STR156##                 n.sub.D.sup.24                                                                 1.5653                 278 "       "   "           2-F, 4-Cl, 5-COOC.sub.2 H.sub.4 OCH.sub.3                                                                  93.5-94.5              279 "       "   "                                                                                           ##STR157##                  99-102                280 "       "   "           2-F, 4-Cl, 5-COOCH.sub.2 COOC.sub.2 H.sub.5                                                                n.sub.D.sup.26.5                                                               1.5739                 281 "       "   "                                                                                           ##STR158##                   109-111.5            282 "       "   "           2-F, 4-Cl, 5-COOCH.sub.3    117-119                283 "       "   "           2-F, 4-Cl, 5-COOH           227-230                284 "       "   "           4-Cl, 5-COOH                206 dec.               285 "       "   "           4-Cl                        93-96                  286 "       "   "           2-F, 4-Cl                   65-67                  287 "       "   "           2-F, 4-OCH.sub.3              72-73.5              288 "       "   "           2-OCH.sub.3, 4-F            94-96                  289 "       "   "           2-F, 4-OCH.sub.2 CCH        n.sub.D.sup.24                                                                 1.6070                 290 "       "   "                                                                                           ##STR159##                 129-130                291 "       "   "                                                                                           ##STR160##                 n.sub.D.sup.25                                                                 1.5642                 292 "       "   "                                                                                           ##STR161##                 124-125                293 "       "   "                                                                                           ##STR162##                 94-96                  294 "       "   "                                                                                           ##STR163##                 47-50                  295 "       "   5,6-(CH.sub.3).sub.2                                                                       4-Cl                        130-132                                (cis)                                                          296 "       "   5,6-(CH.sub.3).sub.2                                                                       4-Cl                        89-90                                  (trans)                                                        297 "       "   6-C.sub.2 H.sub.5                                                                          4-Cl                        105-115                298 "       "   "           2-F, 4-Cl                   n.sub.D.sup.23                                                                 1.5819                 299 "       "   "           2-F, 4-Br                   49-50                  300 "       "   "           2,4,6-F.sub.3               93-94                  301 "       "   6-C.sub.3 H.sub.7                                                                          4-Cl                        107-111                302 "       "   6-CH.sub.3                                                                                  ##STR164##                 143-144                303 "       "   "           2-F, 4-Cl, 5-NH.sub.2       n.sub.D.sup. 26                                                                1.6347                 304 "       "   "           2-F, 4-Cl, 5-NHCH.sub.2 CCH 46-49                  305 "       "   "           2-F, 4-Cl, 5-NHCOCF.sub.3   153-156                306 "       "   "           2-F, 4-Cl, 5-NO.sub.2       108-110                307 "       "   "                                                                                           ##STR165##                 n.sub.D.sup.27.5                                                               1.5870                 308 "       "   "                                                                                           ##STR166##                 146-147                309 "       "   "                                                                                           ##STR167##                 147-148                310 "       "   6,6-(CH.sub.3).sub.2                                                                        ##STR168##                 62-65                  311 "       "   6-CH.sub.3                                                                                  ##STR169##                 68-71                  312 "       "   "           2-F, 4-Cl, 5-OC.sub.12 H.sub.25                                                                            n.sub.D.sup.26.5                                                               1.5442                 313 "       "   "           2-F, 4-Cl, 5-O.sup.i C.sub.3 H.sub.7                                                                       n.sub.D.sup.28                                                                 1.5872                 314 "       "   "           2-F, 4-Cl, 5-OC.sub.3 H.sub.7                                                                              n.sub.D.sup.22.5                                                               1.5891                 315 "       "   "           2-F, 4-Cl, 5-OC.sub.4 H.sub.9                                                                              n.sub.D.sup.23                                                                 1.5942                 316 "       "   "                                                                                           ##STR170##                 n.sub.D.sup.22                                                                 1.6010                 317 "       "   "                                                                                           ##STR171##                 n.sub.D.sup.27                                                                 1.5740                 318 "       "   "                                                                                           ##STR172##                 n.sub.D.sup.27                                                                 1.5680                 319 "       "   "                                                                                           ##STR173##                 n.sub.D.sup.24.5                                                               1.5610                 320 "       "   "                                                                                           ##STR174##                 71-73                  321 "       "   6-C.sub.2 H.sub.5                                                                           ##STR175##                 68-70                  322 "       "   6-CH.sub.3                                                                                  ##STR176##                 n.sub.D.sup.28                                                                 1.5770                 323 "       "   6-C.sub.2 H.sub.5                                                                           ##STR177##                 n.sub.D.sup.28                                                                 1.5792                 324 "       "   6-CH.sub.3                                                                                  ##STR178##                 n.sub.D.sup.20                                                                 1.5605                 325 "       "   6-C.sub.2 H.sub.5                                                                           ##STR179##                 n.sub.D.sup.21                                                                 1.5560                 326 "       "   6-CH.sub.3                                                                                  ##STR180##                 n.sub.D.sup.28                                                                 1.5580                 327 "       "   6-C.sub.2 H.sub.5                                                                           ##STR181##                 n.sub.D.sup.28                                                                 1.5591                 328 "       "   6-CH.sub.3                                                                                  ##STR182##                 110-112                329 "       "   "                                                                                           ##STR183##                 n.sub.D.sup.20                                                                 1.5583                 330 "       "   "                                                                                           ##STR184##                 n.sub.D.sup.15                                                                 1.5764                 331 "       "   "                                                                                           ##STR185##                 n.sub.D.sup.26.5                                                               1.5601                 332 "       "   "                                                                                           ##STR186##                 71-73                  333 "       "   "                                                                                           ##STR187##                 n.sub.D.sup.22.5                                                               1.5860                 334 "       "   "                                                                                           ##STR188##                 n.sub.D.sup.28.5                                                               1.5921                 335 "       "   "                                                                                           ##STR189##                 n.sub.D.sup.22                                                                 1.5878                 336 "       "   "                                                                                           ##STR190##                 n.sub.D.sup.23                                                                 1.5783                 337 "       "   "                                                                                           ##STR191##                 n.sub.D.sup.28                                                                 1.5688                 338 "       "   "                                                                                           ##STR192##                 n.sub.D.sup.28                                                                 1.5619                 339 "       "   "                                                                                           ##STR193##                 n.sub.D.sup.27                                                                 1.5886                 340 "       "   "                                                                                           ##STR194##                 n.sub.D.sup.28                                                                 1.5971                 341 "       "   "                                                                                           ##STR195##                 158-160                342 "       "   "                                                                                           ##STR196##                 n.sub.D.sup.24.5                                                               1.5663                 343 "       "   "                                                                                           ##STR197##                 56-60                  344 "       "   "                                                                                           ##STR198##                 149-153                345 "       "   6-C.sub.2 H.sub.5                                                                           ##STR199##                 n.sub.D.sup.17.5                                                               1.5698                 346 "       "   6-CH.sub.3                                                                                  ##STR200##                 n.sub.D.sup.27                                                                 1.5608                 347 "       "   "                                                                                           ##STR201##                 134-137                348 "       "   "                                                                                           ##STR202##                 109-113                349 "       "   "                                                                                           ##STR203##                 118-121                350 "       "   "                                                                                           ##STR204##                 50-53                  351 "       "   "                                                                                           ##STR205##                 135-138                352 "       "   "                                                                                           ##STR206##                 155-158                353 "       "   "                                                                                           ##STR207##                 58-59                  354 "       "   "                                                                                           ##STR208##                 n.sub.D.sup.22                                                                 1.5669                 355 "       "   "                                                                                           ##STR209##                 116-117                356 "       "   "                                                                                           ##STR210##                   108-108.5            357 "       "   6-C.sub.2 H.sub.5                                                                           ##STR211##                 92-93                  358 "       "   6-CH.sub.3                                                                                  ##STR212##                 n.sub.D.sup.20.5                                                               1.5456                 359 "       "   "                                                                                           ##STR213##                 n.sub.D.sup.26                                                                 1.5870                 360 "       "   "                                                                                           ##STR214##                 n.sub.D.sup.27                                                                 1.5696                 361 "       "   "                                                                                           ##STR215##                 147-149                362 "       "   "                                                                                           ##STR216##                 n.sub.D.sup.23                                                                 1.5901                 363 "       "   6,6-(CH.sub.3).sub.2                                                                        ##STR217##                 n.sub.D.sup.26                                                                 1.5675                 364 "       "   6-C.sub.2 H.sub.5                                                                           ##STR218##                 n.sub.D.sup.20.5                                                               1.5682                 365 "       "   "                                                                                           ##STR219##                 n.sub.D.sup.21.5                                                               1.5492                 366 "       "   6-C.sub.3 H.sub.7                                                                           ##STR220##                 n.sub.D.sup.24                                                                 1.5572                 367 "       "   6-CH.sub.3                                                                                  ##STR221##                 n.sub.D.sup.28                                                                 1.5569                 368 "       "   6-C.sub.2 H.sub.5                                                                           ##STR222##                 n.sub.D.sup.21.5                                                               1.5399                 369 "       "   6-CH.sub.3                                                                                  ##STR223##                 77-78                  370 "       "   "                                                                                           ##STR224##                 n.sub.D.sup.20.5                                                               1.5680                 371 "       "   6-C.sub.2 H.sub.5                                                                           ##STR225##                 n.sub.D.sup.25                                                                 1.5620                 372 "       "   6-CH.sub.3                                                                                  ##STR226##                 n.sub.D.sup.20.5                                                               1.5635                 373 "       "   "                                                                                           ##STR227##                 n.sub.D.sup.24                                                                 1.5579                 374 "       "   "                                                                                           ##STR228##                 n.sub.D.sup.26                                                                 1.5554                 375 "       "   "                                                                                           ##STR229##                  98-100                376 "       "   "                                                                                           ##STR230##                 n.sub.D.sup.19                                                                 1.5960                 377 "       "   "                                                                                           ##STR231##                 75-77                  378 "       "   "                                                                                           ##STR232##                 n.sub.D.sup.21.5                                                               1.5751                 379 "       "   "                                                                                           ##STR233##                 101-102                380 "       "   "                                                                                           ##STR234##                 n.sub.D.sup.27.5                                                               1.5540                 381 "       "   6,6-(CH.sub.3).sub.2                                                                        ##STR235##                 n.sub.D.sup.26                                                                 1.5850                 382 "       "   6-CH.sub.2 OCH.sub.3                                                                        ##STR236##                 n.sub.D.sup.27                                                                 1.5809                 383 "       "   6-C.sub.2 H.sub.5                                                                           ##STR237##                 n.sub.D.sup.26                                                                 1.5785                 384 "       "   6-C.sub.3 H.sub.7                                                                           ##STR238##                 n.sub.D.sup.24                                                                 1.5652                 385 "       "   5-C.sub.2 H.sub.5                                                                           ##STR239##                 n.sub.D.sup.27                                                                 1.5775                 386 "       "   6-CH.sub.3                                                                                  ##STR240##                 n.sub.D.sup.21                                                                 1.5648                 387 "       "   "                                                                                           ##STR241##                 n.sub.D.sup.26.5                                                               1.5778                 388 "       "   "                                                                                           ##STR242##                 n.sub.D.sup.24                                                                 1.5634                 389 "       "   "                                                                                           ##STR243##                 n.sub.D.sup.24                                                                 1.5613                 390 "       "   "                                                                                           ##STR244##                 n.sub.D.sup.19                                                                 1.5701                 391 "       "   "                                                                                           ##STR245##                 n.sub.D.sup.24                                                                 1.5613                 392 "       "   "                                                                                           ##STR246##                 n.sub.D.sup.30.5                                                               1.5841                 393 "       "   6-C.sub.2 H.sub.5                                                                           ##STR247##                 n.sub.D.sup.28                                                                 1.5820                 394 "       "   6-CH.sub.3                                                                                  ##STR248##                 113-115                395 "       "   "                                                                                           ##STR249##                 104-106                396 "       "   "                                                                                           ##STR250##                 n.sub.D.sup.26                                                                 1.5683                 397 "       "   6-C.sub.2 H.sub.5                                                                           ##STR251##                 n.sub.D.sup.26                                                                 1.5883                 398 "       "   6-CH.sub.3                                                                                  ##STR252##                 n.sub.D.sup.22                                                                 1.5884                 399 "       "   "                                                                                           ##STR253##                 n.sub.D.sup.24                                                                 1.5773                 400 "       "   "                                                                                           ##STR254##                 n.sub.D.sup.22                                                                 1.5864                 401 "       "   "                                                                                           ##STR255##                 n.sub.D.sup.22                                                                 1.6042                 402 "       "   "                                                                                           ##STR256##                 n.sub.D.sup.26                                                                 1.5778                 403 "       "   6-C.sub.2 H.sub.5                                                                           ##STR257##                 n.sub.D.sup.27                                                                 1.5836                 404 "       "   6-CH.sub.3                                                                                  ##STR258##                 136-138                405 "       "   6,6-(CH.sub.3).sub.2                                                                        ##STR259##                 210-212                406 "       "   6-C.sub.2 H.sub.5                                                                           ##STR260##                 142-144                407 "       "   6-CH.sub.3                                                                                  ##STR261##                 215-220 dec.           408 "       "   6-C.sub.2 H.sub.5                                                                           ##STR262##                 78-85                  409 "       "   6-CH.sub.3                                                                                  ##STR263##                 49-51                  410 "       "   "                                                                                           ##STR264##                 n.sub.D.sup.26                                                                 1.6080                 411 "       "   "                                                                                           ##STR265##                 n.sub.D.sup.26                                                                 1.5985                 412 "       "   "                                                                                           ##STR266##                 n.sub.D.sup.26.5                                                               1.5512                 413 "       "   "                                                                                           ##STR267##                 111- 112               414 "       "   6-C.sub.2 H.sub.5                                                                           ##STR268##                 n.sub.D.sup.22                                                                 1.6091                 415 "       "   6-CH.sub.3                                                                                  ##STR269##                 n.sub.D.sup.23                                                                 1.6011                 416 "       "   "           2-F, 4-Cl, 5-OCH(COOC.sub.2 H.sub.5).sub.2                                                                 n.sub.D.sup.29.5                                                               1.5512                 417 "       "   6-C.sub.2 H.sub.5                                                                          2-F, 4-Cl, 5-OCH(COOC.sub.2 H.sub.5).sub.2                                                                 n.sub.D.sup.29                                                                 1.5540                 418 "       "   6-CH.sub.3                                                                                  ##STR270##                 n.sub.D.sup.26                                                                 1.5910                 419 "       "   "                                                                                           ##STR271##                  99-101                420 "       "   "                                                                                           ##STR272##                 138-140                421 "       "   "                                                                                           ##STR273##                 n.sub.D.sup.24                                                                 1.5825                 422 "       "   "                                                                                           ##STR274##                 90-93                  423 "       "   "                                                                                           ##STR275##                 31-34                  424 "       "   "                                                                                           ##STR276##                 n.sub.D.sup.27                                                                 1.5881                 425 "       "   "                                                                                           ##STR277##                 n.sub.D.sup.27                                                                 1.5861                 426 "       "   "                                                                                           ##STR278##                 175-181                427 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 CCCH.sub.3                                                                          150-151                428 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 CCCl n.sub.D.sup.26.5                                                               1.6135                 429 "       "   --          2-F, 4-Cl, 5-OCH.sub.2 CCH  139-140                430 "       "   6-CH.sub.3  "                           109-113                431 "       "   "           2-F, 4,5-(OCH.sub.2 CCH).sub.2                                                                             122.5-123.5            432 "       "   "           2,4-F.sub.2, 5-OCH.sub.2 CCH                                                                               n.sub.D.sup.28.5                                                               1.5855                 433 "       "   "           2,4-F.sub.2, 6-Cl, 5-OCH.sub.2 CCH                                                                         n.sub.D.sup.28                                                                 1.5742                 434 "       "   "           2-F, 4-OCH.sub.3, 5-OCH.sub.2 CCH                                                                          158-160                435 "       "   "           2-F, 4-Br, 5-OCH.sub.2 CCH  108-110                436 "       "   "           4-Cl, 5-OCH.sub.2 CCH       110-111                437 "       "   "           2-Br, 4-Cl, 5-OCH.sub.2 CCH 123-125                438 "       "   6,6-(CH.sub.3).sub.2                                                                       2-F, 4-Cl, 5-OCH.sub.2 CCH  105-108                439 "       "   5,6-(CH.sub.3).sub.2 (cis)                                                                 2-F, 4-Cl, 5-OCH.sub.2 CCH  122-123                440 "       "   5,6-(CH.sub.3).sub.2 (trans)                                                               2-F, 4-Cl, 5-OCH.sub.2 CCH  118-119                441 "       "   6-CH.sub.2 OCH.sub.3                                                                       2-F, 4-Cl, 5-OCH.sub.2 CCH  n.sub.D.sup.28                                                                 1.6015                 442 "       "   6-CH.sub.2 O.sup.i C.sub.3 H.sub.7                                                         2-F, 4-Cl, 5-OCH.sub.2 CCH  n.sub.D.sup.28                                                                 1.5950                 443 "       "   6-C.sub.2 H.sub.5                                                                          2-F, 4-Br, 5-OCH.sub.2 CCH  111-113                444 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 C CH 121-122                445 "       "   6-C.sub.3 H.sub.7                                                                          2-F, 4-Cl, 5-OCH.sub.2 CCH  113-115                446 "       "   5-C.sub.2 H.sub.5                                                                          2-F, 4-Cl, 5-OCH.sub.2 CCH  n.sub.D.sup.27                                                                 1.6022                 447 "       "   6-CH.sub.3  2-F, 4-Cl, 5-OCH.sub.2 CBrCBrCH.sub.3                                                                      n.sub.D.sup.26.5                                                               1.6160                 448 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 CF.sub.3                                                                            83.5-85                449 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 CH.sub.2 Br                                                                         94-96                  450 "       "   "           2-F, 4-Cl, 5-OC.sub.3 H.sub.6 CN                                                                           103-104                451 "       "   "           2-F, 4-Cl, 5-OC.sub.3 H.sub.6 COOC.sub.2                                       H.sub.5                     n.sub.D.sup.25.5                                                               1.5735                 452 "       "   "                                                                                           ##STR279##                 n.sub.D.sup.20.5                                                               1.6238                 453 "       "   "                                                                                           ##STR280##                 n.sub.D.sup.20                                                                 1.6275                 454 "       "   "           2-F, 4-Cl, 5-OC.sub.2 H.sub.4 OC.sub.2                                         H.sub.4 OCH.sub.3           52-53                  455 "       "   "                                                                                           ##STR281##                 n.sub.D.sup.18                                                                 1.6157                 456 "       "   "           2-F, 4-Cl, 5-OC.sub.2 H.sub.4 OCH.sub.3                                                                      90-90.5              457 "       "   "           2-F, 4-Cl, 5-OC.sub.2 H.sub.4 OCOCH.sub.3                                                                  n.sub.D.sup.22                                                                 1.5810                 458 "       "   "                                                                                           ##STR282##                 128-130                459 "       "   "                                                                                           ##STR283##                 157-158                460 "       "   "                                                                                           ##STR284##                 112-114                461 "       "   "                                                                                           ##STR285##                 120-121                462 "       "   "                                                                                           ##STR286##                 154-155                463 "       "   "                                                                                           ##STR287##                 110-112                464 "       "               2-F, 4-Cl, 5-OC.sub.2 H.sub.4 SCH.sub.2                                        COOCH.sub.3                 105-107                465 "       "   "                                                                                           ##STR288##                 n.sub.D.sup.21.6                                                               1.6262                 466 "       "   "           2-F, 4-Cl, 5-OC.sub.2 H.sub.4 SCH.sub.3                                                                    n.sub.D.sup.26                                                                 1.6086                 467 "       "   "                                                                                           ##STR289##                 n.sub.D.sup.22                                                                 1.6320                 468 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 CHCCl.sub.2                                                                         85-87                  469 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 CHCH.sub.2                                                                          n.sub.D.sup.27                                                                 1.6035                 470 "       "   "           2,4-F.sub.2, 5-OCH.sub.2 CHCH.sub.2                                                                        n.sub.D.sup.28.5                                                               1.5965                 471 "       "   6-C.sub.2 H.sub.5                                                                          2-F, 4-Br, 5-OCH.sub.2 CHCH.sub.2                                                                          n.sub.D.sup.22.5                                                               1.6172                 472 "       "   6-CH.sub.3  2-F, 4-Cl, 5-OCH.sub.2 CHCHCOOC.sub.2                                                                      n.sub.D.sup. 25.5                                                              1.5905                 473 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 CHCHCl                                                                              94-95                  474 "       "   6-C.sub.2 H.sub.5                                                                          2-F, 4-Cl, 5-OCH.sub.2 CHCHCl                                                                              78-81                  475 "       "   6-CH.sub.3  2-F, 4-Cl, 5-OCH.sub.2 CN   n.sub.D.sup.24                                                                 1.5675                 476 "       "   6-C.sub.2 H.sub.5                                                                          2-F, 4-Br, 5-OCH.sub.2 CN   n.sub.D.sup.23                                                                 1.6153                 477 "       "   6-CH.sub.3  2-F, 4-Cl, 5-OCH.sub.2 COCH.sub.3                                                                          106-108                478 "       "   "                                                                                           ##STR290##                 n.sup.28 1.5838        479 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 COOCH.sub.2 CHClCH.sub.                                 2 Cl                        172-177                                                                        dec.                   480 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 COOCH.sub.3                                                                         125-128                481 "       "   "                                                                                           ##STR291##                 91-93                  482 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 OC.sub.2 H.sub.5                                                                    n.sub.D.sup.20.5                                                               1.5929                 483 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 OCH.sub.3                                                                           70-72                  484 "       "   "                                                                                           ##STR292##                 50-52                  485 "       "   6-C.sub.2 H.sub.5                                                                           ##STR293##                 n.sub.D.sup.21                                                                 1.5790                 486 "       "   6-CH.sub.3                                                                                  ##STR294##                 n.sub.D.sup.26                                                                 1.6005                 487 "       "   "                                                                                           ##STR295##                 209-210 dec.           488 "       "   "                                                                                           ##STR296##                 n.sub.D.sup.28                                                                 1.6308                 489 "       "   "                                                                                           ##STR297##                 176-177                490 "       "   "                                                                                           ##STR298##                 101-102                491 "       "   "                                                                                           ##STR299##                 156-157                492 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 SCH.sub.2 CHCH.sub.2                                                                n.sub.D.sup.21                                                                 1.5999                 493 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 SCH.sub.2 COOCH.sub.3                                                               n.sub.D.sup.19.5                                                               1.5973                 494 "       "   "                                                                                           ##STR300##                 n.sub.D.sup.20.5                                                               1.6181                 495 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 SCH.sub.3                                                                           69-71                  496 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 SO.sub.2 CH.sub.3                                                                   56-59                  497 "       "   "                                                                                           ##STR301##                 65-67                  498 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 SOCH.sub.3                                                                          43-46                  499 "       "   "                                                                                           ##STR302##                 166-168 dec.           500 "       "   "                                                                                           ##STR303##                 n.sub.D.sup.29                                                                 1.6420                 501 "       "   "                                                                                           ##STR304##                 n.sub.D.sup.26                                                                 1.6220                 502 "       "   "                                                                                           ##STR305##                 n.sub.D.sup.25.5                                                               1.6270                 503 "       "   "                                                                                           ##STR306##                 n.sub.D.sup.26                                                                 1.6371                 504 "       "   "                                                                                           ##STR307##                 n.sub.D.sup.20.5                                                               1.6290                 505 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 Si(CH.sub.3).sub.3                                                                  39-42                  506 "       "   "           2-F, 4,5-(OCH.sub.3).sub.2  127-128                507 "       "   6-C.sub.2 H.sub.5                                                                          2-F, 4-Cl, 5-OCH.sub.3      87-89                  508 "       "   6-CH.sub.3  2,4-Cl.sub.2, 5-OCH.sub.2 CCH                                                                              123-124                509 "       "   "                                                                                           ##STR308##                 47-49                  510 "       "   "                                                                                           ##STR309##                 92-94                  511 "       "   6,6-(CH.sub.3).sub.2                                                                        ##STR310##                 n.sub.D.sup.24                                                                 1.5600                 512 "       "   6-CH.sub.3  2-F, 4-Cl, 5-OCOCH.sub.3    155-158                513 "       "   6-C.sub.2 H.sub.5                                                                          2-F, 4-Cl, 5-OCOCH.sub.3    136-137                514 "       "   "                                                                                           ##STR311##                 54-56                  515 "       "   6-CH.sub.3  2-F, 4-Cl, 5-OH             164-166                516 "       "   6-C.sub.2 H.sub.5                                                                          2-F, 4-Cl, 5-OH             137-139                517 "       "   6-CH.sub.3                                                                                  ##STR312##                 n.sub.D.sup.27.5                                                               1.5869                 518 "       "   "                                                                                           ##STR313##                 77-80                  519 "       "   "                                                                                           ##STR314##                 n.sub.D.sup.20.5                                                               1.5985                 520 "       "   6-C.sub.2 H.sub.5                                                                           ##STR315##                 112-114                521 CH.sub.2                                                                               "   "           2-F, 4-Cl, 5-CH.sub.2 CN    113-114                522 "       "   "           2-F, 4-Cl, 5-CH.sub.2 COOC.sub.2 H.sub.5                                                                   n.sub.D.sup.20                                                                 1.5855                 523 "       "   "           2-F, 4-Cl, 5-CH.sub.2 COOCH.sub.2 CCH                                                                      n.sub.D.sup.20.5                                                               1.5992                 524 "       "   "                                                                                           ##STR316##                 75-77                  525 "       "   "           2-F, 4-Cl, 5-CHCHCOOC.sub.2 H.sub.5                                                                          147-148.5            526 "       "   "                                                                                           ##STR317##                 147-149                527 "       "   "           2-F, 4-Cl, 5-CHCHCOOCH.sub.2 C CH                                                                          116.5-117.5            528 "       "   6-CH.sub.3  2-F, 4-Cl, 5-CHCHCOOCH.sub.3                                                                               161-164                529 "       "   "           2-F, 4-Cl, 5-CHCHCOOH       205-207                530 "       "   "           2-F, 4-Cl, 5-CHCHCOONa      257-260                531 "       "   "           2-F, 4-Cl,                  161-163                                             ##STR318##                                        532 "       "   "                                                                                           ##STR319##                 97-98                  533 "       "   "                                                                                           ##STR320##                 134-135                534 "       "   "                                                                                           ##STR321##                 n.sub.D.sup.21.5                                                               1.5820                 535 "       "   "                                                                                           ##STR322##                 133.5-135              536 "       "   "                                                                                           ##STR323##                 71-72                  537 "       "   "           2-F, 4-Cl, 5-COO.sup.t C.sub.4 H.sub.9                                                                     89-90                  538 "       "   "           4-Cl, 5-COOC.sub.2 H.sub.5  n.sub.D.sup.23                                                                 1.6150                 539 "       "   "           2-F, 4-Cl, 5-COOC.sub.2 H.sub.5                                                                            88-90                  540 "       "   "           2-OCH.sub.3, 4-Cl, 5-COOC.sub.2 H.sub.5                                                                    77-79                  541 "       "   "           2-F, 4-Cl, 5-COOC.sub.3 H.sub.7                                                                            101-102                542 "       "   "                                                                                           ##STR324##                   66-67.5              543 "       "   "                                                                                           ##STR325##                  85-86.5               544 "       "   "                                                                                           ##STR326##                 78- 80                 545 "       "   "                                                                                           ##STR327##                 58-60                  546 "       "   "                                                                                           ##STR328##                 n.sub.D.sup.19.5                                                               1.6066                 547 "       "   "           2-F, 4-Cl, 5-COO.sup.i C.sub.3 H.sub.7                                                                     90-91                  548 "       "   "           2-F, 5-COO.sup.i C.sub.3 H.sub.7                                                                           107.5-108.5            549 "       "   "                                                                                           ##STR329##                 78-80                  550 "       "   "                                                                                           ##STR330##                 89.5-91                551 "       "   "                                                                                           ##STR331##                 87-88                  552 "       "   "                                                                                           ##STR332##                 91-93                  553 "       "   "                                                                                           ##STR333##                   110-111.5            554 "       "   "           2-F, 4-Cl,                  n.sub.D.sup.22.5                                                               1.5671                                             5-COOC.sub.2 H.sub.4 OC.sub.2 H.sub.4                                          OC.sub.2 H.sub.4 OCH.sub.3                         555 "       "   "           2-F, 4-Cl, 5-COOC.sub.2 H.sub.4 (OC.sub.2                                      H.sub.4).sub.3 OCH.sub.3    n.sub.D.sup.22.5                                                               1.5596                 556 "       "   "           2-F, 4-Cl, 5-COOC.sub.3 H.sub.6(OC.sub.3                                       H.sub.6 ) .sub.7OCH.sub.3   n.sub.D.sup.21.5                                                               1.5115                 557 "       "   "           2-F, 4-Cl, 5-COOCH.sub.2 Si(CH.sub.3).sub.3                                                                 98-101                558 "       "   "           4-Cl, 5-COOCH.sub.3         101-102                559 "       "   "           2-F, 4-Cl, 5-COOCH.sub.3      99-100.5             560 "       "   "           4-Cl, 5-COOH                229 dec.               561 "       "   "           2-F, 4-Cl, 5-COOH           210-213                562 "       "   "                                                                                           ##STR334##                   118-119.5            563 "       "   "           2-F, 4-Cl, 5-COONa          285-286                564 "       "   "                                                                                           ##STR335##                 n.sub.D.sup.26                                                                 1.6210                 565 "       "   "                                                                                           ##STR336##                 n.sub.D.sup.22                                                                 1.6036                 566 "       "   --                                                                                          ##STR337##                 91-92                  567 "       "   6-OCH.sub.3                                                                                 ##STR338##                 n.sub.D.sup.28                                                                 1.6001                 568 "       "   "                                                                                           ##STR339##                 59-60                  569 "       "   "                                                                                           ##STR340##                   70-70.5              570 "       "   "                                                                                           ##STR341##                 91.5-92                571 "       "   "                                                                                           ##STR342##                 76-78                  572 "       "   "                                                                                           ##STR343##                 118-120                573 "       "   "                                                                                           ##STR344##                 77-80                  574 "       "   "                                                                                           ##STR345##                 75-78                  575 "       "   "                                                                                           ##STR346##                 64-67                  576 "       "   "           2-F, 4-Cl, 5-O.sup.i C.sub.3 H.sub.7                                                                       n.sub.D.sup.28                                                                 1.6012                 577 "       "   "                                                                                           ##STR347##                 128-129                578 "       "   "                                                                                           ##STR348##                 n.sub.D.sup.21.5                                                               1.5912                 579 "       "   --                                                                                          ##STR349##                 124-126                580 "       "   6-CH.sub.3                                                                                  ##STR350##                 85-86                  581 "       "   "                                                                                           ##STR351##                 n.sub.D.sup.20.5                                                               1.5879                 582 "       "   "                                                                                           ##STR352##                 n.sub.D.sup.20.5                                                               1.6100                 583 "       "   "                                                                                           ##STR353##                 n.sub.D.sup.20                                                                 1.5989                 584 "       "   "                                                                                           ##STR354##                 n.sub.D.sup.20.5                                                               1.6003                 585 "       "   "                                                                                           ##STR355##                 n.sub.D.sup.20.5                                                               1.6205                 586 "       "   "                                                                                           ##STR356##                 n.sub.D.sup.22                                                                 1.5837                 587 "       "   "                                                                                           ##STR357##                 93-95                  588 "       "   "                                                                                           ##STR358##                 108-110                589 "       "   "                                                                                           ##STR359##                 98.5-99.5              590 "       "   "                                                                                           ##STR360##                 n.sub.D.sup.22.5                                                               1.5751                 591 "       "   "                                                                                           ##STR361##                 115-116                592 "       "   "                                                                                           ##STR362##                 143.5-144              593 "       "   "                                                                                           ##STR363##                 n.sub.D.sup.23.5                                                               1.5450                 594 "       "   "                                                                                           ##STR364##                 61.5-62.5              595 "       "   6-C.sub.2 H.sub.5                                                                           ##STR365##                 81-82                  596 "       "   6-CH.sub.3                                                                                  ##STR366##                 n.sub.D.sup.19.5                                                               1.5687                 597 "       "   "                                                                                           ##STR367##                 103-104                598 "       "   "                                                                                           ##STR368##                 71-72                  599 "       "   "                                                                                           ##STR369##                 n.sub.D.sup.20.5                                                               1.5640                 600 "       "   --                                                                                          ##STR370##                 107-109                601 "       "   6-CH.sub.3                                                                                  ##STR371##                   116-116.5            602 "       "   6,6-(CH.sub.3).sub.2                                                                        ##STR372##                 n.sub.D.sup.23                                                                 1.5814                 603 "       "   6-C.sub.2 H.sub.5                                                                           ##STR373##                 92-94                  604 "       "   6-CH.sub.3                                                                                  ##STR374##                 58.5-60.5              605 "       "   "                                                                                           ##STR375##                 n.sub.D.sup.22.5                                                               1.5711                 606 "       "   "                                                                                           ##STR376##                 n.sub.D.sup.18.5                                                               1.5946                 607 "       "   "                                                                                           ##STR377##                 n.sub.D.sup.22.5                                                               1.5929                 608 "       "   "                                                                                           ##STR378##                 n.sub.D.sup.20                                                                 1.5615                 609 "       "   "                                                                                           ##STR379##                 73-75                  610 "       "   "                                                                                           ##STR380##                 n.sub.D.sup.21                                                                 1.5957                 611 "       "   "                                                                                           ##STR381##                 103-105                612 "       "   "                                                                                           ##STR382##                 n.sub.D.sup.19.5                                                               1.5804                 613 "       "   "                                                                                           ##STR383##                 142-143                614 "       "   "                                                                                           ##STR384##                 134.5-135              615 "       "   "                                                                                           ##STR385##                 81-83                  616 "       "   "                                                                                           ##STR386##                 110-112                617 "       "   --          2-F, 4-Cl, 5-OCH.sub.2 CCH    104-106.5            618 "       "   6-CH.sub.3  2-F, 4-Cl, 5-OCH.sub.2 CCH  129-130                619 "       "   6-C.sub.2 H.sub.5                                                                          2-F, 4-Cl, 5-OCH.sub.2 C CH 149-150                620 "       "   6-CH.sub.3  2-F, 4-Cl, 5-(OC.sub.2 H.sub.4) .sub.3OCH.sub.                                 3                           n.sub.D.sup.17.5                                                               1.5740                 621 "       "   "           2-F, 4-Cl, 5-(OC.sub.2 H.sub.4 ) .sub.4OCH.sub                                 .3                          n.sub.D.sup.19.5                                                               1.5572                 622 "       "   "                                                                                           ##STR387##                 n.sub.D.sup.26                                                                 1.6132                 623 "       "   "                                                                                           ##STR388##                 82-83                  624 "       "   "                                                                                           ##STR389##                 130-131                625 "       "   "                                                                                           ##STR390##                 127-128                626 "       "   "                                                                                           ##STR391##                 102-103                627 "       "   "                                                                                           ##STR392##                 79-80                  628 "       "   "           2-F, 4-Cl, 5-OC.sub.2 H.sub.4 OCH.sub.3                                                                    69-70                  629 "       "   "           2-F, 4-Cl, 5-OC.sub.2 H.sub.4 OCHCH.sub.2                                                                  61-62                  630 "       "   "           2-F, 4-Cl, 5-OC.sub.2 H.sub.4 OCONHCH.sub.3                                                                102-103                631 "       "   "           2-F, 4-Cl, 5-OC.sub.2 H.sub.4 OH                                                                             65-65.5              632 "       "   "                                                                                           ##STR393##                 96-97                  633 "       "   "                                                                                           ##STR394##                 121-123                634 "       "   "                                                                                           ##STR395##                  98-100                635 "       "   "                                                                                           ##STR396##                 87-88                  636 "       "   "                                                                                           ##STR397##                 71-72                  637 "       "   "                                                                                           ##STR398##                 87-88                  638 "       "   "                                                                                           ##STR399##                 96-97                  639 "       "   "                                                                                           ##STR400##                 96-97                  640 "       "   "                                                                                           ##STR401##                 85-86                  641 "       "   "                                                                                           ##STR402##                 117-118                642 "       "   "                                                                                           ##STR403##                 105-107                643 "       "   "                                                                                           ##STR404##                   136-137.5            644 "       "   "                                                                                           ##STR405##                 74-75                  645 "       "   "                                                                                           ##STR406##                 46-47                  646 "       "   "                                                                                           ##STR407##                 124-125                647 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 CHCCl.sub.2                                                                         112-113                648 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 CHCHCOOC.sub.2                                                                      n.sub.D.sup.19.5                                                               1.5865                 649 "       "   "                                                                                           ##STR408##                 113-115                650 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 COOC.sub.2 H.sub.5                                                                  141-143                651 "       "   "                                                                                           ##STR409##                 142-144                652 "       "   "           2-F, 4-Cl, (HCl salt)       150-151                653 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 COO.sup.i C.sub.3                                       H.sub.7                     115-117                654 "       "   "                                                                                           ##STR410##                 71-74                  655 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 COOCH.sub.2 CCH                                                                     140-142                656 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 COOCH.sub.2 CHCH.sub.2                                                              97-99                  657 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 COOCH.sub.2 CHClCH.sub.                                 2 Cl                        107-110                658                                                                                 ##STR411##                                                                            "   --          2-F, 4-Cl, 5-OCH.sub.2 COOCH.sub.3                                                                         104.5-105              659 CH.sub.2                                                                               "   6-CH.sub.3  2-F, 4-Cl, 5-OCH.sub.2 COOCH.sub.3                                                                         124-126                660 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 COOH 162-163                661 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 OC.sub.2 H.sub.5                                                                    44-45                  662 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 OCH.sub.3                                                                           68-69                  663 "       "   "                                                                                           ##STR412##                 82-83                  664 "       "   "                                                                                           ##STR413##                 101-102                665 "       "   6-C.sub.2 H.sub.5                                                                           ##STR414##                 106-108                666 "       "   6-CH.sub.3  2-F, 4-Cl, 5-OCHCHCH.sub.2 COOC.sub.2                                                                      n.sub.D.sup.19.5                                                               1.5975                 667 "       "   "                                                                                           ##STR415##                 137-139                668 "       "   "                                                                                           ##STR416##                 159-160                669 "       "   "           2-F, 4-Cl, 5-OH             161-163                670 "       "   "           2-F, 4-Cl, 5-OH, 6-I        58-60                  671 "       "   "                                                                                           ##STR417##                 107-109                672                                                                                 ##STR418##                                                                            "   --          4-Cl                        250 up                 673                                                                                 ##STR419##                                                                            "   --          4-Cl                        94-97                  674                                                                                 ##STR420##                                                                            "   --          2-F, 4-Cl, 5-OCH.sub.2 CCH  130-132                675 "       "   --                                                                                          ##STR421##                 75-78                  676 "       "   --                                                                                          ##STR422##                   138-138.5            677 CH.sub.2 S                                                                             "   --          4-Cl                        120-122                678                                                                                 ##STR423##                                                                            "   --          2-F, 4-Cl                    97-100                679 CH.sub.2 CH.sub.2                                                                      "   --                                                                                          ##STR424##                   79-80.5              680 "       "   --          2-F, 4-Cl, 5-OCH.sub.2 COOCH.sub.3                                                                         101-103                681 CH.sub.2                                                                               "   6-CH.sub.3  2-F, 4-Cl, 5-COOC(CH.sub.3).sub.2 COOCH.sub.3                                                              117-119                682 O       "   "                                                                                           ##STR425##                 173-176                683 CH.sub.2                                                                               "   "                                                                                           ##STR426##                 83-84                  684 "       "   "                                                                                           ##STR427##                 158-160                685 "       "   "                                                                                           ##STR428##                 142.5 -143.5           686 "       "   "                                                                                           ##STR429##                 115.5-117              687 "       "   "           2-F, 4-Cl, 5-COOCH(COOC.sub.2                                                                                118-119.5b.2         688 "       "   "                                                                                           ##STR430##                                        689 "       "   "           2-F, 4-Cl, 5-COOC.sub.2 H.sub.4 (OC.sub.2                                      H.sub.4).sub.6 OCH.sub.3    n.sub.D.sup.20.5                                                               1.5429                 690 O       "   "                                                                                           ##STR431##                 173-175                691 "       "   "                                                                                           ##STR432##                 n.sub.D.sup.21.5                                                               1.5767                 692 "       "   "           2-F, 4-Cl, 5-COO.sup.t C.sub.4 H.sub.9                                                                     124-126                693 CH.sub.2                                                                               "   "                                                                                           ##STR433##                   145-146.5            694 "       "   "           2-F, 4-Cl, 5-COOCH.sub.2 CHCHCOOC.sub.2                                        H.sub.5                     115-116                695 "       "   "           2-F, 4-Cl, 5-COOC.sub.3 H.sub.6 COOC.sub.2                                     H.sub.5                     52-53                  696 CH.sub.2                                                                               "   "                                                                                           ##STR434##                 199.5-201              697 CH.sub.2 CH.sub.2                                                                      "   --                                                                                          ##STR435##                 111-112                698                                                                                 ##STR436##                                                                            "   6.6-(CH.sub.3).sub.2                                                                       2-F, 4-Cl, 5-OCH.sub.2 COOCH.sub.3                                                                         108.5-109              699 CH.sub.2                                                                               "   "                                                                                           ##STR437##                 124-125                700 O       "   "                                                                                           ##STR438##                 n.sub.D.sup.18.5                                                               1.6119                 701 CH.sub.2                                                                               "   "                                                                                           ##STR439##                 96-99                  702 "       "   "                                                                                           ##STR440##                 121.5-122.5            703 O       "   "                                                                                           ##STR441##                 118-120                704 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 OCH.sub.2 CCH                                                                       72-73                  705 CH.sub.2                                                                               "   "           2-F, 4-Cl, 5-OCHCHCOOC.sub.2 H.sub.5                                                                       72-73                  706 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 SCH.sub.3                                                                           n.sub.D.sup.24.5                                                               1.6135                 707 "       "   "           2-F, 4-Cl, 5-SCH.sub.2 COO.sup.i C.sub.3                                       H.sub.7                     79-82                  708 "       "   "           2,4-F.sub.2, 3-OCH.sub.2 CCH                                                                               n.sub.D.sup.24.5                                                               1.5936                 709 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 OCH.sub.2 OCH.sub.3                                                                 n.sub.D.sup.26                                                                 1.5840                 710 "       "   "           2,4-F.sub.2, 3-COOC.sub.2 H.sub.5                  711 "       "   "                                                                                           ##STR442##                 135-137                712 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 OCH.sub.2 CHCH.sub.2                                                                42-43                  713 "       "   "           2-F, 4-Cl, 5-CF.sub.3       80-81                  714 "       "   "                                                                                           ##STR443##                 45-50                  715 "       "   "                                                                                           ##STR444##                                        716 "       "   "           2-F, 4-Cl, 5-COCH.sub.3     93-94                  717 "       "   "                                                                                           ##STR445##                 n.sub.D.sup.24.5                                                               1.5605                 718 "       "   "                                                                                           ##STR446##                 89-93                  719 "       "   "                                                                                           ##STR447##                 92-96                  720 "       "   "                                                                                           ##STR448##                 n.sub.D.sup.23.5                                                               1.5608                 721 "       "   "                                                                                           ##STR449##                 114-115                722 "       "   "                                                                                           ##STR450##                 158-170                723 "       "   "                                                                                           ##STR451##                 n.sub.D.sup.24.5                                                               1.5685                 724 "       "   "           2-F, 5-COOH                 213-214                725 "       "   "           2-F, 5-COO.sup.t C.sub.4 H.sub.9                                                                             113-114.5            726 O       "   "           2-F, 4-Cl, 5-CN             136-138                727 CH.sub.2                                                                               "   "           2-F, 4-Cl, 5-CN             167.5-169              728 "       "   "           2-F, 4-Cl, 5-COS.sup.i C.sub.3 H.sub.7                                                                     n.sub.D.sup.25.5                                                               1.6195                 729 "       "   "           2-F, 4-Cl, 5-COCH(OCH.sub.3).sub.2                                                                         89-90.5                730 O       "   "                                                                                           ##STR452##                 n.sub.D.sup.24.5                                                               1.5647                 731 CH.sub.2                                                                               "   "                                                                                           ##STR453##                 n.sub.D.sup.24.5                                                               1.5900                 732 "       "   "                                                                                           ##STR454##                 74-76                  733 "       "   "                                                                                           ##STR455##                 n.sub.D.sup.24                                                                 1.6080                 734 O       "   "                                                                                           ##STR456##                 n.sub.D.sup.24                                                                 1.5850                 735 CH.sub.2                                                                               "   "                                                                                           ##STR457##                 n.sub.D.sup.24                                                                 1.6530                 736 O       "   "                                                                                           ##STR458##                 153-154                737 CH.sub.2                                                                               "   "                                                                                           ##STR459##                 105-106                738 "       "   "           2-F, 4-Cl, 5-OCH.sub.2 S.sup.i C.sub.3                                         H.sub.7                     66.5-67                739 O       "   "           2-F, 4-Cl, 5-OCH.sub.2 S.sup.i C.sub.3                                         H.sub.7                     64-65                  740 CH.sub.2                                                                               "   "           2-F, 4-Cl, 5-SCH.sub.2 COOH *.sup.1                741 CH.sub.2 S                                                                             "   6CH.sub.2   2-F, 4-Cl, 5-OCH.sub.2 CCH  *.sup.2                742 CH.sub.2                                                                               "   6-CH.sub.3  2-F, 4-Cl, 5-SO.sub.2 N(CH.sub.3).sub.2                                                                    111-113                743 "       "   "                                                                                           ##STR460##                 n.sub.D.sup.28                                                                 1.6000                 __________________________________________________________________________      *.sup.1 HNMR (90 MHz) (in CDCl.sub.3) δ 1.3 (3H, d), 2.1-2.6 (1H,        m), 2.7-3.2 (2H, m), 3.2-3.6 (1H, m), 3.9-4.2 (1H, m), 3.65 (2H, s ), 6.8      (1H, d), 7.1 (1H, d)                                                           *.sup.2 HNMR (270 MHz) (in CDCl.sub.3) δ 2.60 (1H, t), 3.72 (2H, s)      4.58 (2H, s), 4.75 (2H, d), 5.20 (2H, d), 6.86 (1H, d), 7.22 (1H, d)     

As mentioned previously, the compounds possess superior herbicidal activity. The compounds may be applied directly to the soil as pre-emergence treatment or to plant foliage as post-emergence treatment, or they can be mixed intimately with soil. The compounds may be applied to soil or to plant foliage in amount of 1 g or more per 10 are.

A herbicidal composition having a compound of this invention as its active ingredient may be formulated by mixing suitable carriers in a form generally used in agricultural chemicals such as wettable powder, water soluble powder, glanule, emulsifiable concentrate and flowable. As solid carriers, talc, white carbon, bentonite, clay, diatomaceous earth or the like may be used. As liquid carriers, water, alcohol, benzene, xylene, kerosene, mineral oil, cyclohexane, cyclohexanone, dimethylformamide or the like may be used. A surface active agent may, if necessary, be added in order to give a homogeneous and stable formulation.

Compounds can also be applied admixed with other chemicals, which are used in agronomic and horticultural management and which are compatible with such compounds. Such chemicals can be, but are not restricted to, the classes of chemical commonly known as fungicides, insecticides, acaricides, herbicides and plant growth regulators. In particular, by mixing it with the other herbicides, its applied dosage and manpower can be decreased and furthermore, the higher effect by synergetic function of both chemicals can be expected.

For admixture of the compound with known herbicides, the use is recommended of benthiocarb, molinate, MY-93 (S-2,2-dimethylbenzil) 1-piperidinecarbothioate) or other carbamate-type herbicides; thiocarbamate-type herbicides; butachlor, pretilachlor or other acid amide-type herbicides; chlormethoxynil, bifenox or other diphenylether-type herbicides; pyrazolate, pyrazoxyfen or other pyrazole-type herbicides; chlorsulfuron, sulfometuron or other sulfonylurea-type herbicides; MCP, MCPB or other phenoxy alkane carboxylic acid-type herbicides; diclofop-methyl or other phenoxy propionic acid-type herbicides; fluazifopbutyl or other pyridyloxyphenoxypropionic acid-type herbicides; piperophos, dymron, bentazon, oxadiazon, NTN-801 (2-benzothiazole-2-yloxy-N-methyl acetoanilide), naproanilid, HW-52 (4-ethoxymethoxybenzo-2',3'-dichloroanilide), KNW-242 (1-(3-methylphenyl)-5-phenyl-1H-1,2,4-triazole-3-carboxamide), S47 (N-(α,α-dimethylbenzil)-d-bromotertiary butyl acetoamide, sethoxydim, alloxydim-sodium and other cyclohexanedione-type herbicides. These herbicides in various combinations may also be mixed with a vegetable oil or an oil concentrate.

The concentration of the active ingredient in a herbicidal composition may vary according to type of formulation, and the concentration is, for example, in the range of 5-80 weight percent, preferably 30-60 weight percent, in wettable powder; 70-95 weight percent, preferably 80-90 weight percent, in water soluble powder; 5-70 weight percent, preferably 10-40 weight percent, in emulsifiable concentrate; 10-70 weight percent, preferably 20-50 weight percent, in flowable; 0.5-10 weight percent, preferably 1-5 weight percent, in glanule.

A wettable powder, a water soluble powder or an emulsifiable concentrate thus produced may be diluted with water to a specified concentration and used as a liquid suspension or a liquid emulsion for treating soils or plant foliage. Further, a flowable and a glanule may be directly used for soil or foliage treatment, otherwise, it may be diluted with water to a specified concentration and used as a liquid suspension for treating soils or plant foliage.

Non-limiting examples of herbicidal composition are illustrated by the following tests:

    ______________________________________                                         Example 21 Wettable powder                                                                   parts by weight                                                  ______________________________________                                         Compound No. 683                                                                               50                                                             White carbon    12                                                             Diatomaceoua earth                                                                             30                                                             Sodium alkylsulfate                                                                             8                                                             ______________________________________                                    

These are mixed homogeneously and reduced to fine particles to provide a wettable powder containing 50% of active ingredient. In use, it is diluted to a desired concentration with water, and is sprayed as suspension.

    ______________________________________                                         Example 22 Emulsifiable concentrace                                                              parts by weight                                              ______________________________________                                         Compound No. 430    40                                                         Xylene              35                                                         Dimethylformamide   15                                                         Polyoxyethylene phenyl ether                                                                       10                                                         ______________________________________                                    

These are mixed and dissolved to provide an emulsifiable concentrate containing 40% of active ingredient. In use, it is diluted to a desired concentration with water, and sprayed as an emulsion.

    ______________________________________                                         Example 23 Flowable                                                                                parts by weight                                            ______________________________________                                         Compound No. 609      30                                                       Sun spray-7N (commcrcial product of                                                                  60                                                       Sun Oil Co., Ltd.)                                                             Polyoxyethylene alkylether                                                                            5                                                       Sorbitan alkylate      5                                                       ______________________________________                                    

These are mixed homogeneously to provide a flowable containing 30% of active ingredient.

    ______________________________________                                         Example 24 Glanule                                                                           parts by weight                                                  ______________________________________                                         Compound No. 197                                                                                3                                                             Talc            40                                                             Clay            40                                                             Bentonite       10                                                             Sodium alkyl sulfate                                                                            7                                                             ______________________________________                                    

These are mixed homogeneously to provide a glanule containing 3% of active ingredient.

The herbicidal effects of compounds are illustrated by the following tests:

Test 1

Paddy field test

Seeds of barnyardgrass (Echinochloa crus-galli), duck-tongue weed (Monochoria vaginalis), bulrush (Scirpus Hotarui) and small-flower umbrella plant (Cyperus difformis) were planted 0.2-0.5 cm in depth in plastic pots (15 cm depth and 14 cm diameter) containing paddy field soil, and two rice plants (variety: Nihonbare) at 2-3 leaf stage were transplanted. Next day pots were watered 2-3 cm in depth. Immediately granules of each compounds of this invention were applied at the dosage described in the table. The pots were kept in a greenhouse.

Three weeks after treatment, the degree of damage of the each plants was observed and evaluated on the scale of value of 0-10, which has the following meanings.

    ______________________________________                                         Index       Degree of damage                                                   ______________________________________                                         0           0%                                                                 2           20-29%                                                             4           40-49%                                                             6           60-69%                                                             8           80-89%                                                             10          100                                                                ______________________________________                                    

Index 1, 3, 5, 7 and 9 mean the intermediate degree between 0 and 2, 2 and 4, 4 and 6, 6 and 8, 8 and 10 respectively. ##EQU1## The results are shown in Table 2.

                  TABLE 2                                                          ______________________________________                                         Application                                                                    Rate of                                                                        Active      Degree of Damage                                                   Ingredient  Rice                                                               (g/10 a)    plant  B.G.*.sup.1                                                                            D.T.W.*.sup.2                                                                         B.R.*.sup.3                                                                          S.U.P.*.sup.4                          ______________________________________                                         Com-                                                                           pound                                                                          No.                                                                             10   50        1      4     10     10    10                                    13   50        1      10    10     10    10                                    15   50        1      0     10     10    10                                    28   50        0      5     10     10    10                                    54   50        0      3     10     9      8                                    73   50        0      0     10     10     9                                   106   50        0      10    10     10    10                                   115   50        0      9     10     10    10                                   117   50        0      9     10     10    10                                   119   25        0      10    10     10    10                                   123   50        0      10    10     10    10                                   127   25        0      10    10     10    10                                   133   50        0      10    10     10    10                                   134   50        0      9     10     10    10                                   138   50        1      8     10     8     10                                   142   50        0      3     10     10    10                                   151   50        3      9     10     9     10                                   182   50        0      4     10     10    10                                   188   50        0      6     10     9     10                                   194   25        1      10    10     10    10                                   196   50        0      10    10     10    10                                   197   50        0      10    10     10    10                                   199   50        0      9     10     10    10                                   202   50        0      4     10     10    10                                   205   50        0      10    10     10    10                                   207   25        0      9     10     10    10                                   209   50        1      9     10     10    10                                   212   25        0      0     10     10    10                                   213   50        1      10    10     10    10                                   214   50        1      10    10     10    10                                   216   50        1      9     10     10    10                                   219   50        0      10    10     9     10                                   220   50        0      3     10     10    10                                   223   50        0      8     10     7      9                                   224   50        0      10    10     10    10                                   227   25        0      4     10     10    10                                   231   50        1      9     10     10    10                                   234   50        0      0     10     10    10                                   239   25        0      7     10     10     9                                   241   50        0      10    10     10    10                                   251   50        0      3     10     10     9                                   256   50        0      9     10     10    10                                   258   25        0      3     10     10     8                                   263   50        0      10    10     7     10                                   270   50        1      8     10     10    10                                   292   50        0      2     10     5      8                                   304   50        2      3     10     9      7                                   309   50        0      1     10     10    10                                   316   50        1      10    10     10    10                                   318   50        0      10    10     10    10                                   328   50        0      10    10     10    10                                   331   50        0      0     10     10    10                                   335   50        0      10    10     10    10                                   341   50        0      3     10     10    10                                   345   25        0      2     10     10    10                                   350   50        0      10    10     10    10                                   361   50        0      6     10     10    10                                   368   25        0      0     10     10    10                                   378   50        1      7     10     10    10                                   381   50        0      0     10     9     10                                   386   50        2      9     10     3     10                                   396   50        1      8     10     10    10                                   398   50        1      4     10     10    10                                   409   50        0      2     10     9      9                                   415   50        0      7     10     10    10                                   418   50        0      2     10     10    10                                   421   50        2      7     10     10    10                                   430   25        1      10    10     10    10                                   438   25        1      10    10     10    10                                   439   25        0      5     10     10    10                                   444   25        0      10    10     10    10                                   458   50        0      10    10     7     10                                   461   50        0      10    10     10    10                                   465   50        1      10    10     10    10                                   483   50        2      10    10     10    10                                   487   25        0      0      9     3      9                                   494   50        0      10    10     8     10                                   505   50        0      10    10     5     10                                   511   50        0      3     10     10    10                                   514   50        0      2     10     10    10                                   527   50        0      4     10     8      9                                   565   50        2      10    10     10    10                                   574   50        1      10    10     10    10                                   580   50        0      10    10     10    10                                   584   50        0      10    10     4     10                                   589   50        1      3     10     10    10                                   616   50        1      10    10     10    10                                   618   50        0      10    10     10    10                                   623   50        1      10    10     10    10                                   629   50        0      3     10     10    10                                   636   50        1      10    10     8     10                                   663   50        0      4     10     7     10                                   668   50        0      8     10     5     10                                   674   50        0      5     10     10    10                                   693   50        0      10    10     8     10                                   697   50        0      10    10     3     10                                   711   50        0      10    10     6     10                                   716   50        0      7     10     9     10                                   730   50        0      4     10     3     10                                   Com-                                                                           para-                                                                          tive                                                                           Com-                                                                           pound                                                                          *(1)  100       0      4      8     4      1                                   (2)   100       0      1      2     1      2                                   ______________________________________                                          *.sup.1 : B.G.-- barnyardgrass                                                 *.sup.2 : D.T.W.--ducktongue weed                                              *.sup.3 : B.R.--bulrush                                                        *.sup.4 : S.U.P.--smallflower umbrella plant                                   *(1)                                                                           ##STR461##                                                                     (2)                                                                            ##STR462##                                                               

Test 2

Postemergence treatment test

Seeds of lambsquarter (Chenopodium album), pigweed (Amaranthus retroflexus), sedge (Cyperus microiria) and soybean were planted in clay pots (12 cm depth and 16 cm diameter) containing clay loam soil and were allowed to grow in greenhouse. When the plants were grown to a 3-10 cm height, aqueous suspensions, prepared by diluting an emulsifiable concentrate with water to specified concentration (500 ppm) were sprayed on the foliage of the plants at a rate of 100 1/10 a by using a micro-sprayer. Three weeks after treatment the degree of damage of the each plants was observed and evaluated on the same scale as in Test 1. The results are shown in Table 3.

                  TABLE 3                                                          ______________________________________                                                 Application                                                                    Rate of Ac-                                                                    tive Ingre-                                                            Compound                                                                               dient      Degree of Damage                                            No.     (g/10 a)   Soybean  L.Q.*.sup.5                                                                          P.W.*.sup.6                                                                           S.D.*.sup.7                           ______________________________________                                          11     50         5        10    10     10                                     14     25         3        10    10     10                                    124     25         2        10    9      10                                    125     50         3        10    10     10                                    139     50         1        10    10     10                                    140     25         1        10    7      10                                    150     25         2        9     10     10                                    152     25         4        10    8      8                                     153     25         1        7     8      7                                     157     50         2        10    9      7                                     161     25         2        9     9      8                                     171     25         1        10    10     9                                     173     50         5        10    10     10                                    175     50         3        10    9      10                                    176     50         2        10    10     10                                    183     25         1        8     9      8                                     190     25         2        9     7      7                                     243     50         5        9     10     10                                    245     25         1        5     9      8                                     266     25         3        10    10     10                                    269     25         6        10    10     10                                    272     25         4        10    10     10                                    274     50         4        10    10     10                                    277     25         1        7     10     9                                     279     25         2        10    10     10                                    281     25         3        10    9      10                                    282     50         5        10    10     10                                    320     50         2        9     10     10                                    325     25         3        10    10     10                                    330     25         3        10    10     10                                    353     25         4        10    10     10                                    356     25         5        8     10     9                                     358     25         1        8     10     8                                     360     50         2        10    10     10                                    365     50         3        10    10     10                                    366     25         3        10    10     10                                    369     25         4        10    10     10                                    374     25         3        10    10     10                                    376     25         4        10    9      9                                     379     50         5        10    10     10                                    387     25         4        10    10     10                                    390     25         2        9     9      9                                     391     25         2        9     10     9                                     393     50         4        10    10     10                                    394     25         1        9     8      8                                     399     25         6        10    7      8                                     404     25         5        10    10     10                                    410     50         4        10    7      9                                     411     25         2        9     9      8                                     419     25         5        10    10     7                                     420     25         7        10    10     10                                    449     50         6        10    10     10                                    456     25         9        9     10     9                                     477     25         3        8     8      5                                     480     50         6        10    10     10                                    492     25         4        10    10     10                                    510     25         3        10    10     10                                    522     50         3        10    10     10                                    532     50         4        l0    10     10                                    533     50         2        10    10     10                                    535     50         7        10    10     10                                    536     25         2        10    10     10                                    537     50         4        10    10     10                                    544     50         4        10    10     10                                    545     50         4        10    10     10                                    546     50         2        10    10     10                                    550     50         7        10    10     10                                    555     50         3        10    10     10                                    561     50         4        10    10     10                                    562     50         2        10    10     10                                    568     50         4        10    10     10                                    569     50         3        10    10     10                                    571     50         4        10    10     10                                    572     50         2        10    10     10                                    591     50         1        10    10     10                                    592     50         2        7     6      5                                     593     25         2        9     9      8                                     595     25         5        10    10     10                                    597     25         3        10    10     10                                    598     25         4        10    10     10                                    604     25         4        10    10     10                                    605     25         4        10    10     10                                    606     25         2        10    10     10                                    607     50         6        10    10     10                                    608     25         5        10    9      9                                     609     25         1        10    10     10                                    610     25         5        10    9      9                                     611     25         5        10    10     10                                    612     50         3        10    10     10                                    613     50         2        10    10     10                                    626     50         6        10    10     10                                    632     25         7        10    10     10                                    635     50         8        10    10     10                                    638     25         4        10    10     10                                    641     50         7        10    10     10                                    646     50         7        10    10     10                                    650     50         2        10    10     10                                    653     50         1        10    10     10                                    659     50         1        10    10     10                                    660     50         5        10    10     10                                    665     25         6        9     8      9                                     683     25         2        10    10     10                                    686     50         10       10    10     10                                    689     50         8        10    10     10                                    690     50         8        10    10     10                                    691     50         10       10    10     10                                    694     50         3        10    10     10                                    707     25         1        10    10     10                                    718     50         6        10    10     10                                    719     25         2        10    10     10                                    720     25         2        10    10     10                                    721     50         3        10    10     10                                    725     50         1        6     9      7                                     728     50         6        10    10     10                                    730     50         9        10    10     10                                    733     50         8        10    10     10                                    Compara-                                                                       tive                                                                           Compound                                                                       *(1)    400        4        3     3      4                                     (2)     400        3        0     1      2                                     ______________________________________                                         *.sup.5 L.Q. . . . lambsquater                                                 *.sup.6 P.W. . . . pigweed                                                     *.sup.7 S.D. . . . sedge                                                        *(1)                                                                                    The same compound as shown in Table 2                                (2)                                                                        

What we claim is:
 1. A compound having the formula ##STR463## wherein each of r¹, r², r³ and R⁴ represents hydrogen, C₁₋₄ alkyl which may be substituted by C₁₋₃ alkoxy, phenyl or methylthio, or phenyl which may be substituted by halogen or methyl, and such r¹, r², r³ and r⁴ may form alkylidene, and at least two of r¹, r², r³ and r⁴ are hydrogen; andR represents same or different substituent(s) selected from the group consisting of halogen, nitro, cyano, --G--R¹, ##STR464## dimethyl sulfamoyl and --L; and n represents an integer of 1 to 5; andwherein G represents --O--, --S--, ##STR465## in which r¹⁰ represents hydrogen or C₂₋₃ alkynyl; and R¹ represents hydrogen, ##STR466## quinoxalinyl which may be substituted by halogen, thiadiazolyl which may be substituted by methyl, pyridyl, 1,3,5-triazinyl, which may be substituted by halogen or methylamino, thiazolyl, tetrahydropyranyl, or --T; and K represents oxygen or sulfur; and R² represents hydrogen, metal corresponding to one valency, C₁₋₃ alkylidene amino or --U; and each of R³ and R⁴ represents hydrogen, C₁₋₃ alkyl, C₂₋₃ alkynyl or C₁₋₂ alkoxy; and R⁵ represents phenyl or C₁₋₃ alkyl which may be substituted by methoxy; and R⁶ represents hydrogen, or C₁₋₂ alkyl, which may be substituted by C₁₋₂ alkoxycarbonyl; and R⁷ represents hydrogen or methyl; and --L represents phenyl which may be substituted by methyl, C₂₋₃ alkenyl which may be substituted by ##STR467## C₂₋₅ alkynyl, or C₁₋₃ alkyl which may be substituted by halogen, hydroxy, cyano, ##STR468## methoxy, acetyloxy or ##STR469## and wherein r¹¹ represents methyl; and each of r¹² and r¹³ represents C₁₋₂ alkyl; and r¹⁴ represents C₁₋₃ alkyl or phenyl which may be substituted by methyl; and r¹⁵ represents C₁₋₃ alkyl which may be substituted by halogen or C₁₋₂ alkoxycarbonyl or phenyl which may be substituted by halogen; and each of r¹⁶ and r¹⁷ represents hydrogen or C₁₋₂ alkyl; and --T represents C₁₋₁₂ alkyl which may be substituted by halogen, C₃₋₆ cycloalkyl (which may be substituted by halogen), cyano, phenyl (which may be substituted by halogen, nitro, cyano, methyl or methoxy), --Q--r²¹, acethyloxy, trimethylsilyl, ##STR470## --(OC₂ H₄ --₂ OCH₃, --(OC₂ H₄ --₃ OCH₃ isoxazolyl (which may be substituted by methyl), oxadiazolyl (which may be substituted by C₁₋₃ alkyl), pyrazolyl, or pyrydyl, C₃₋₆ cycloalkyl which may be substituted by propargyl or halogen, C₃₋₄ alkenyl which may be substituted by halogen or ethoxycarbonyl, C₃₋₈ alkynyl which may be substituted by halogen or phenyl, or phenyl which may be substituted by halogen, trifluoromethyl or ethoxycarbonylethoxy; and --U represents C₁₋₈ alkyl which may be substituted by cyclopropyl, halocyclopropyl, cyano, C₁₋₄ alkoxycarbonyl, methoxy, phenoxy, phenylthio, trimethylsilyl or --O(CH₂)_(gh) --Or²⁸, C₂₋₄ alkenyl which may be substituted by C₁₋₃ alkoxycarbonyl or propargyl which may be substituted by phenyl; and r¹⁸ represents hydrogen, metal corresponding to one valency, C₁₋₇ alkyl or propargyl; andwherein Q represents --O-- or --S(O)_(k) --(k=0, 1 or 2); and r²¹ represents hydrogen, C₁₋₂ alkyl, which may be substituted by phenyl, methoxy or phenoxy, C₁₋₂ alkoxycarbonyl, vinyl, phenyl which may be substituted by halogen, nitro, methoxy, methyl, trifluoromethyl or methylendioxy, naphthyl, pyrydyl which may be substituted by methyl or methylcarbamoyl; and W represents oxygen or sulfur; and r²² represents hydrogen, metal corresponding to one valency, C₁₋₃ alkylidene amino, allyl, C₃₋₅ alkynyl, phenyl or C₁₋₁₀ alkyl which may be substituted by halogen, C₁₋₃ alkoxy C₂₋₃ alkenyloxy, benzyloxy, phenyl which may be substituted by methoxy, methylthio, phenoxy, allylthio, benzylthio or phenylthio, C₁₋₂ alkoxycarbonyl, methoxycarbonylmethylthio, furyl, isoxazolyl which may be substituted by methyl, trimethylsilyl or cyano; and Z represents oxygen or sulfur; and each of r²³ and r²⁴ represents hydrogen, ethoxy, allyloxy, cyclohexylcarbamoyl, C₁₋₄ alkyl radical which may be substituted by C₁₋₂ alkoxy phenyl or C₁₋₂ alkoxycarbonyl, allyl, propargyl, cyclohexyl or phenyl; and r²⁵ represents methyl, phenyl or morpholino; and r²⁶ represents hydrogen, allyl or acetyl which may be substituted by halogen; and r²⁷ represents amino, methyl or phenyl; and g represents an integer of 1 to 3; and h represents an integer of 2 to 7; and r²⁸ represents methyl;or a salt thereof with an organic or inorganic acid.
 2. A herbicidal composition comprising an inert carrier and an effective amount of a compound of claim
 1. 3. A process for the control of the weeds comprising applying to the locus to be protected an effective amount of a compound of claim
 1. 